Two-cycle engine oils containing alkyl phenols

ABSTRACT

Lubricating oils are described which are useful in two-cycle engines. These oils contain a minor amount of at least one phenolic compound of the general formula 
     
         (R).sub.a --Ar--(OH).sub.b 
    
     wherein R is a substantially saturated, hydrocarbon-based group of an average of at least 10 aliphatic carbon atoms; a and b are each independently an integer of one up to three times the number of aromatic nuclei present in Ar with the proviso that the sum of a and b does not exceed the unsatisfied valences of Ar; and Ar is a single ring, a fused ring or a linked polynuclear moiety having 0 to 3 optional substituents consisting of lower alkyl, lower alkoxyl, methylol or lower hydrocarbon-based substituted methylol, halo and combinations of two or more of said optional substituents.

BACKGROUND OF THE INVENTION

(1) Field of the Invention

This invention relates to lubricant compositions containing a majoramount of an oil of lubricating viscosity and a minor amount of at leastone alkyl phenol. The lubricants are useful in two-cycle internalcombustion engines. More particularly, the invention relates to suchoils containing alkyl phenols having at least one hydrocarbon-basedgroup of at least about 10 aliphatic carbon atoms. Since two-cycleengine oils are often combined with fuels before or during use, thisinvention also relates to two-cycle fuel-lubricant mixtures.

(2) Prior Art

A variety of phenolic compounds have been described which are useful aslubricant and fuel additives. Alkylated amino phenols have beendescribed in U.S. Pat. No. 4,320,021 as being useful as additives forlubricants and fuels. Amino phenol and detergent/dispersant combinationshave been described in U.S. Pat. No. 4,200,545 as being useful inlubricating compositions, particularly for two-cycle internal combustionengines and also as additives and lubricant-fuel mixtures for two-cycleengines. Hydrocarbon-substituted methylol phenols are described in U.S.Pat. No. 4,053,428 as useful in lubricants and fuels.

(3) General Background

Over the past several decades the use of spark-ignited two-cycle(two-stroke) internal combustion engines including rotary engines suchas those of the Wankel type has steadily increased. They are presentlyfound in power lawn mowers and other power-operated garden equipment,power chain saws, pumps, electrical generators, marine outboard engines,snowmobiles, motorcycles and the like.

The increasing use of two-cycle engines coupled with increasing severityof the conditions in which they have operated has led to an increasingdemand for oils to adequately lubricate such engines. Among the problemsassociated with lubrication of two-cycle engines are piston ringsticking, rusting, lubrication failure of connecting rod and mainbearings and the general formation on the engine's interior surface ofcarbon and varnish deposits. The formation of varnish is a particularlyvexatious problem since the build-up of varnish on piston and cylinderwalls is believed to ultimately result in ring sticking which leads tofailure of the sealing function of piston rings. Such seal failurecauses loss of cylinder compression which is particularly damaging intwo-cycle engines because they depend on suction to draw the new fuelcharge into the exhausted cylinder. Thus, ring sticking can lead todeterioration in engine performance and unnecessary consumption of fueland/or lubricant. Spark plug fouling and engine port plugging problemsalso occur in two-cycle engines.

The unique problems and techniques associated with the lubrication oftwo-cycle engines has led to the recognition by those skilled in the artof two-cycle engine lubricants as a distinct lubricant type. See, forexample, U.S. Pat. Nos. 3,085,975; 3,004,837; and 3,753,905.

The invention described herein is directed to minimizing these problemsthrough the provision of effective additives for two-cycle engine oilsand oil-fuel combinations which eliminate or reduce engine varnishdeposits and piston ring seal failure.

SUMMARY OF THE INVENTION

This invention comprises a lubricant composition for two-cycle enginescomprising a major amount by weight of at least one oil of lubricatingviscosity and a minor amount of weight of at least one phenolic compoundof the formula

    (R).sub.a --Ar--(OH).sub.b                                 Formula I

wherein R is a substantially saturated hydrocarbon-based group of anaverage at least 10 aliphatic carbon atoms; a and b are suchindependently an integer of one up to three times the number of aromaticnuclei present in Ar with the proviso that the sum of a and b does notexceed the unsatisfied valences of Ar; and Ar is a single ring, a fusedring or a linked polynuclear aromatic moiety having 0 to 3 optionalsubstituents consisting of lower alkyl, lower alkoxyl, methylol or lowerhydrocarbon-based substituted methylol, halo and combinations of two ormore of said optional substituents.

The term "phenol" is used in this specification in its art-acceptedgeneric sense to refer to hydroxy-aromatic compounds having at least onehydroxyl group bonded directly to a carbon of an aromatic ring.

Lubricating oil-fuel mixtures for two-cycle engines and methods forlubricating two-cycle engines including Wankel engines are also withinthe scope of this invention.

DESCRIPTION OF THE INVENTION The Oils of Lubricating Viscosity

The two-cycle engine oil compositions of this invention comprise a majoramount of an oil of lubricating viscosity. Typically this viscosity isin the range of about 2.0 to about 150 cst at 19.9° C., more typicallyin the range of about 5.0 to about 130 cst at 98.9° C.

These oils of lubricating viscosity can be natural or synthetic oils.Mixtures of such oils are also often useful.

Natural oils include mineral lubricating oils such as liquid petroleumoils and solvent-treated or acid-treated mineral lubricating oils of theparaffinic, naphthenic or mixed paraffinic-naphthenic types. Oils oflubricating viscosity derived from coal or shale are also useful baseoils.

Synthetic lubricating oils include hydrocarbon oils and halo-substitutedhydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,polybutylenes, polypropylenes, propylene-isobutylene copolymers,chlorinated polybutylenes, etc.); poly(1-hexenes), poly(1-octenes),poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes,di-(2-ethylhexyl)-benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.); alkylated diphenyl ethers andalkylated diphenyl sulfides and the derivatives, analogs and homologsthereof and the like.

Oils made by polymerizing olefins of less than 5 carbon atoms, such asethylene, propylene, butylenes, isobutene, pentene, and mixtures thereofare typical synthetic polymer oils. Methods of preparing such polymeroils are well known to those skilled in the art as is shown by U.S. Pat.Nos. 2,278,445; 2,301,052; 2,318,719; 2,329,714; 2,345,574; and2,422,443.

Alkylene oxide polymers (i.e., homopolymers, interpolymers, andderivatives thereof where the terminal hydroxyl groups have beenmodified by esterification, etherification, etc.) constitute a preferredclass of known synthetic lubricating oils for the purpose of thisinvention, especially for use in combination with alkanol fuels. Theyare exemplified by the oils prepared through polymerization of ethyleneoxide or propylene oxide, the alkyl and aryl ethers of thesepolyoxyalkylene polymers (e.g., methyl polypropylene glycol ether havingan average molecular weight of 1000, diphenyl ether of polyethyleneglycol having a molecular weight of 500-1000, diethyl ether ofpolypropylene glycol having a molecular weight of 1000-1500, etc.) ormono- and polycarboxylic esters thereof, for example, the acetic acidesters, mixed C₃ -C₈ fatty acid esters, or the C₁₃ Oxo acid diester oftetraethylene glycol.

Another suitable class of synthetic lubricating oils comprises theesters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkylsuccinic acids, alkenyl succinic acids, maleic acid, azelaic acid,suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic aciddimer, malonic acid, alkyl malonic acids, alkenyl malonic acids, etc.)with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecylalcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycolmonoether, propylene glycol, etc.). Specific examples of these estersinclude dibutyl adipate, de(2-ethylhexyl)sebacate, di-n-hexyl fumarate,dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctylphthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyldiester of linoleic acid dimer, the complex ester formed by reacting onemole of sebacic acid with two moles of tetraethylene glycol and twomoles of 2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those made from C₅ to C₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Silicon-based oils such as polyalkyl-, polyaryl-, polyalkoxy-, orpolyaryloxy-siloxane oils and silicate oils comprise another usefulclass of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropylsilicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methyl-hexyl)silicate,tetra-(p-tert-butylphenyl)silicate,hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes,poly(methylphenyl)siloxanes, etc.). Other synthetic lubricating oilsinclude liquid esters of phosphorus-containing acids (e.g., tricresylphosphate, trioctyl phosphate, diethyl ester of decane phosphonic acid,etc.), polymeric tetrahydrofurans and the like.

Unrefined, refined and rerefined oils, either natural or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedhereinabove can be used in the lubricant compositions of the presentinvention. Unrefined oils are those obtained directly from a natural orsynthetic source without further purification treatment. For example, ashale oil obtained directly from retorting operations, a petroleum oilobtained directly from primary distillation or ester oil obtaineddirectly from an esterification process and used without furthertreatment would be an unrefined oil. Refined oils are similar to theunrefined oils except they have been further treated in one or morepurification steps to improve one or more properties. Many suchpurification techniques are known to those of skill in the art such assolvent extraction, secondary distillation, acid or base extraction,filtration, percolation, etc. Rerefined oils are obtained by processessimilar to those used to obtain refined oils applied to refined oilswhich have been already used in service. Such rerefined oils are alsoknown as reclaimed or reprocessed oils and often are additionallyprocessed by techniques directed to removal of spent additives and oilbreakdown products.

The Alkyl Phenols: The Aromatic Moiety, Ar

The aromatic moiety, Ar, can be a single aromatic nucleus such as abenzene nucleus, a pyridine nucleus, a thiophene nucleus, a1,2,3,4-tetrahydronaphthalene nucleus, etc., or a polynuclear aromaticmoiety. Such polynuclear moieties can be of the fused type; that is,wherein at least two aromatic nuclei are fused at two points to anothernucleus such as found in naphthalene, anthracene, the azanaphthalenes,etc. Such polynuclear aromatic moieties also can be of the linked typewherein at least two nuclei (either mono or polynuclear) are linkedthrough bridging linkages to each other. Such bridging linkages can bechosen from the group consisting of carbon-to-carbon single bonds, etherlinkages, keto linkages, sulfide linkages, polysulfide linkages of 2 to6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, methylenelinkages, alkylene linkages, di-(lower alkyl)methylene linkages, loweralkylene ether linkages, alkylene keto linkages, lower alkylene sulfurlinkages, lower alkylene polysulfide linkages of 2 to 6 carbon atoms,amino linkages, polyamino linkages and mixtures of such divalentbridging linkages. In certain instances, more than one bridging linkagecan be present in Ar between aromatic nuclei. For example, a fluorenenucleus has two benzene nuclei linked by both a methylene linkage and acovalent bond. Such a nucleus may be considered to have 3 nuclei butonly two of them are aromatic. Normally, Ar will contain only carbonatoms in the aromatic nuclei per se.

The number of aromatic nuclei, fused, linked or both, in Ar can play arole in determining the values of a and b in Formula I. For example,when Ar contains a single aromatic nucleus, a and b are eachindependently 1 to 3. When Ar contains 2 aromatic nuclei, a and b caneach be an integer of 1 to 6 that is, from 1 up to three times thenumber of aromatic nuclei present (e.g., in naphthalene, 2 nuclei). Witha trinuclear Ar moiety, a and b can again each be an integer of 1 to 9.Thus, for example, when Ar is a biphenyl moiety, a and b can eachindependently be an integer of 1 to 6. The values of a and b areobviously limited by the fact that their sum cannot exceed the totalunsatisfied valences of Ar.

The single ring aromatic nucleus which can be the Ar moiety can berepresented by the general formula

    ar(Q).sub.m

wherein ar represents a single ring aromatic nucleus (e.g., benzene) of4 to 10 carbons, each Q independently represents a lower alkyl group,lower alkoxyl group, methylol or lower hydrocarbon-based substitutedmethylol, or halogen atom, and m is 0 to 3. As used in thisspecification and appended claims, "lower" refers to groups having 7 toless carbon atoms such as lower alkyl and lower alkoxyl groups. Halogenatoms include fluorine, chlorine, bromine and iodine atoms; usually, thehalogen atoms are fluorine and chlorine atoms.

Specific examples of such single ring Ar moieties are the following:##STR1## wherein Me is methyl, Et is ethyl, and Pr is n-propyl.

When Ar is a polynuclear fused-ring aromatic moiety, it can berepresented by the general formula

    ar  ar  .sub.m' (Q).sub.mm'

wherein ar, Q and m are as defined hereinabove, m' is 1 to 4 andrepresent a pair of fusing bonds fusing two rings so as to make twocarbon atoms part of the rings of each of two adjacent rings. Specificexamples of fused ring aromatic moieties Ar include: ##STR2##

When the aromatic moiety Ar is a linked polynuclear aromatic moiety itcan be represented by the general formula

    ar(--Lng--ar--).sub.w (Q).sub.mw

wherein w is an integer of 1 to about 20, ar is as described above withthe proviso that there are at least 3 unsatisfied (i.e., free) valencesin the total of ar groups, Q and m are as defined hereinbefore, and eachLng is a bridging linkage individually chosen from the group consistingof carbon-to-carbon single bonds, ether linkages (e.g., --CH₂ --O--CH₂--), keto linkages (e.g., ##STR3## sulfide linkages (e.g., --S--),polysulfide linkages of 2 to 6 sulfur linkages (e.g., --S₂₋₆ --),sulfinyl linkages (e.g., --S(O)--), sulfonyl linkages (e.g., --S(O)₂--), lower alkylene linkages (e.g., --CH₂ --, --CH₂ --CH₂ --,--CH--O(R^(o))H--, etc.), di(lower alkyl)-methylene linkages (e.g.,--CR₂ ^(o)), lower alkylene ether linkages (e.g., --CH₂ O--, --CH₂O--CH₂ --, --CH₂ --CH₂ O--, --CH₂ CH₂ OCH₂ CH₂ --, ##STR4## etc.), loweralkylene keto linkages (e.g., ##STR5## lower alkylene sulfide linkages(e.g., wherein one or more --O--'s in the lower alkylene ether linkagesis replaced with an --S-- atom), lower alkylene polysulfide linkages(e.g., wherein one or more --O--'s is replaced with a --S₂₋₆ group)amino linkages (e.g., ##STR6## --CH₂ N--, --CH₂ NCH₂ --, --alk--N--,where alk is lower alkylene, etc.), polyamino linkages (e.g.,--N(alkN)₁₋₁₀, where the unsatisfied free N valences are taken up with Hatoms or R^(o) groups), and mixtures of such bridging linkages (eachR^(o) being a lower alkyl group).

Specific examples of Ar when it is linked polynuclear aromatic moietyinclude: ##STR7##

Usually all these Ar moeties are unsubstituted except for the R and --OHgroups (and any bridging groups).

For such reasons as cost, availability, performance etc., the Ar moietyis normally a benzene nucleus, lower alkylene bridged benzene nucleus,or a naphthalene nucleus. Thus, a typical Ar moiety is a benzene ornaphthalene nucleus having 3 to 5 unsatisfied valences, so that one ortwo of said valences may be satisfied by a hydroxyl group with theremaining unsatisfied valences being, insofar as possible, either orthoor para to a hydroxyl group. Preferably, Ar is a benzene nucleus having3 to 4 unsatisfied valences so that one can be satisfied by a hydroxylgroup with the remaining 2 or 3 being either ortho or para to thehydroxyl group.

The Substantially Saturated Hydrocarbon-based Group R

The phenolic compounds used in the two-cycle oils of the presentinvention contain, directly bonded to the aromatic moiety Ar, asubstantially saturated monovalent hydrocarbon-based group R of at leastabout 10 aliphatic carbon atoms. This R group preferably contains atleast 30 and up to about 400 aliphatic carbon atoms. More than one suchgroup can be present, but usually, no more than 2 or 3 such groups arepresent for each aromatic nucleus in the aromatic moiety Ar. The totalnumber of R groups present is indicated by the value for "a" in FormulaI. Usually, the hydrocarbon-based group has at least about 30, moretypically, at least about 50 aliphatic carbon atoms and up to about 400,more typically, up to about 300 aliphatic carbon atoms.

Illustrative hydrocarbon based groups containing at least ten carbonatoms are n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl,chlorooctadecyl, triicontanyl, etc. Generally, the hydrocarbon-basedgroups R are made from homo- or interpolymers (e.g., copolymers,terpolymers) of mono- and diolefins having 2 to 10 carbon atoms, such asethylene, propylene, butene-1, isobutene, butadiene, isoprene, 1-hexene,1-octene, etc. Typically, these olefins are 1-monoolefins. The R groupscan also be derived from the halogenated (e.g., chlorinated orbrominated) analogs of such homo- or interpolymers. The R groups can,however, be made from other sources, such as monomeric high molecularweight alkenes (e.g., 1-tetracontene) and chlorinated analogs andhydrochlorinated analogs thereof, aliphatic petroleum fractions,particularly paraffin waxes and cracked and chlorinated analogs andhydrochlorinated analogs thereof, white oils, synthetic alkenes such asthose produced by the Ziegler-Natta process (e.g., poly(ethylene)greases) and other sources known to those skilled in the art. Anyunsaturation in the R groups may be reduced or eliminated byhydrogenation according to procedures known in the art.

As used herein, the term "hydrocarbon-based" denotes a group having acarbon atom directly attached to the remainder of the molecule andhaving a predominantly hydrocarbon character within the context of thisinvention. Therefore, hydrocarbon-based groups can contain up to onenon-hydrocarbon radical for every ten carbon atoms provided thisnon-hydrocarbon radical does not significantly alter the predominantlyhydrocarbon character of the group. Those skilled in the art will beaware of such radicals, which include, for example, hydroxyl, halo(especially chloro and fluoro), alkoxyl, alkyl mercapto, alkyl sulfoxy,etc. Usually, however, the hydrocarbon-based groups R are purelyhydrocarbyl and contain no such non-hydrocarbyl radicals.

The hydrocarbon-based groups R are substantially saturated, that is,they contain no more than one carbon-to-carbon unsaturated bond forevery ten carbon-to-carbon single bonds present. Usually, they containno more than one carbon-to-carbon non-aromatic unsaturated bond forevery 50 carbon-to-carbon bonds present.

The hydrocarbon-based groups of the phenols used in the two-cycle oilsof this invention are also substantially aliphatic in nature, that is,they contain no more than one non-aliphatic moiety (cycloalkyl,cycloalkenyl or aromatic) group of six or less carbon atoms for everyten carbon atoms in the R group. Usually, however, the R groups containno more than one such non-aliphatic group for every fifty carbon atoms,and in many cases, they contain no such non-aliphatic groups at all;that is, the typical R groups are purely aliphatic. Typically, thesepurely aliphatic R groups are alkyl or alkenyl groups.

Specific examples of the substantially saturated hydrocarbon-based Rgroups containing an average of more than 30 carbon atoms are thefollowing:

a mixture of poly(ethylene/propylene) groups of about 35 to about 70carbon atoms

a mixture of the oxidatively or mechanically degradedpoly(ethylene/propylene) groups of about 35 to about 70 carbon atoms

a mixture of poly(propylene/1-hexene) groups of about 80 to about 150carbon atoms

a mixture of poly(isobutene) groups having an average of 50 to 75 carbonatoms

A preferred source of the group R are poly(isobutene)s obtained bypolymerization of a C₄ refinery stream having a butene content of 35 to75 weight percent and isobutene content of 30 to 60 weight percent inthe presence of a Lewis acid catalyst such as aluminum trichloride orboron trifluoride. These polybutenes contain predominantly (greater than80% of total repeating units) isobutene repeating units of theconfiguration ##STR8##

The attachment of the hydrocarbon-based group R to the aromatic moietyAr of the phenols used in the two-cycle oils of this invention can beaccomplished by a number of techniques well known to those skilled inthe art. One particularly suitable technique is the Friedel-craftsreaction, wherein an olefin (e.g., a polymer containing an olefinicbond), or halogenated or hydrohalogenated analog thereof, is reactedwith a phenol. The reaction occurs in the presence of a Lewis acidcatalyst (e.g., boron trifluoride and its complexes with ethers,phenols, hydrogen fluoride, etc., aluminum chloride, aluminum bromide,zinc dichloride, etc.). Methods and conditions for carrying out suchreactions are well known to those skilled in the art. See, for example,the discussion in the article entitled, "Alkylation of Phenols" inKirk-Othmer "Encyclopedia of Chemical Technology", Second Edition, Vol.1, pages 894-895, Interscience Publishers, a division of John Wiley andCompany, N.Y., 1963. Other equally well known appropriate and convenienttechniques for attaching the hydrocarbon-based group R to the aromaticmoiety Ar will occur readily to those skilled in the art.

As will be appreciated from inspection of Formula I, the phenols used inthe two-cycle oils of this invention contain at least one of each of thefollowing substituents: a hydroxyl group and a R group as defined above.Each of the foregoing groups must be attached to a carbon atom which isa part of an aromatic nucleus in the Ar moiety. They need not, however,each be attached to the same aromatic ring if more than one aromaticnucleus is present in the Ar moiety.

The Optional Substituents (R")

As mentioned, the aromatic moiety Ar may contain up to 3 optionalsubstituents which are lower alkyl, lower alkoxyl, methylol or lowerhydrocarbon-based substituted methylol, halo or combinations of two ormore of these optional substituents. These substituents may be attachedto a carbon atom which is part of the aromatic nucleus in Ar. They neednot, however, be attached to the same aromatic ring if more than onering is present in Ar.

A preferred substituent is a methylol or substituted methylol as definedabove. The lower hydrocarbon-based substituents have up to seven carbonatoms and can be alkyl (e.g., methyl, ethyl, etc.), alkenyl (propenyl,etc.), aryl (e.g. phenyl, tolyl), and alkaryl (e.g., benzyl). They canbe represented by "hyd" and the methylol substituents thus can berepresented by --CH₂ OH(methylol), ##STR9## Usually the substituent ismethylol itself or an alkyl-substituted methylol or phenyl-substitutedmethylol substituent, e.g., ##STR10##

The methylol or substituted methylol group can be introduced by reactionof the phenol or alkylated phenol with a hydrocarbon-based aldehyde orfunctional equivalent thereof. Suitable aldehydes include formaldehyde,benzaldehyde, acetaldehyde, butyraldehyde, hydroxy butyraldehyde,hexanals, etc. "Functional equivalents" are materials (e.g., solutions,polymers, hydrates, etc.) which react as aldehydes under the conditionsof the reaction and include such materials as paraformaldehyde,hexamethylenetetramine, paraldehyde, formalin and methylol. Shoulddisubstituted methylol groups be desired, the aldehyde is replaced withan appropriate ketone, such as acetone, methyl ethyl ketone,acetophenone, benzophenone, and the like. Mixtures of aldehydes and/orketones can also be used to produce compounds having mixtures ofmethylol groups.

Formaldehyde and functional equivalents are generally preferred, sincethey yield the preferred methylol groups. Introduction of the methylolgroups usually takes place by reacting the phenolic compound with analdehyde, ketone or functional equivalent thereof in the presence orabsence of an acidic or alkaline reagent. When the reaction takes placein the absence of such reagent, usually a portion of the mixture becomesacidic or alkaline by in situ degradation of the aldehyde or ketone;excess phenol can also fulfill this function.

Generally, however, the reaction of the aldehyde, ketone or functionalequivalent thereof takes place in the presence of an alkaline reagentsuch as an alkali metal or alkaline earth metal oxide, hydroxide orlower alkoxide, at a temperature up to about 160° C. Other alkalinereagents which can be used include sodium carbonate, sodium bicarbonate,sodium acetate, sodium propionate, pyridine, and hydrocarbon-basedamines such as methyl amine and aniline; naturally, mixtures of two ormore bases can be used. Preferably, the reaction takes place in thetemperature range of about 30° to about 125° C.; more usually, it iscarried out between 70° and 100° C.

The relative proportions of phenolic compound and aldehyde, ketone orfunctional equivalent thereof are not critical. It is generallysatisfactory to use 0.1-5 equivalents of aldehyde and about 0.05-10.0equivalents of alkaline reagent per equivalent of phenolic compound. Asused herein, the term "equivalent" when applied to a phenolic compoundindicates the weight of such compound equal to the molecular weightthereof divided by the number of unsubstituted aromatic carbons bearinghydrogen atoms. As applied to the aldehyde, ketone or functionalequivalent thereof, an "equivalent" is the weight required to produceone mole of monomeric aldehyde. An equivalent of alkaline reagent isthat weight of reagent which when dissolved in one liter of solvent(e.g., water) will give a one normal solution. One equivalent ofalkaline reagent will therefore neutralize, i.e., bring to pH7 a onenormal solution of, for example, hydrochloric or sulfuric acid.

It is generally convenient to carry out the reaction of the phenol inthe presence of a substantially inert, organic liquid diluent which maybe volatile or non-volatile. This diluent may dissolve all thereactants, or it may not, but in any event, it does not substantiallyaffect the course of the reaction under the prevailing conditionsthough, in certain cases, it may promote the speed of the reaction byincreasing the contact of the reagents. Suitable diluents includehydrocarbons such as naphtha, textile spirits, benzene, toluene, xylene;mineral oils (which are among the preferred); synthetic oils (asdescribed hereinbelow); alcohols, such as isopropanol, butanol,isobutanol, amyl alcohol, ethyl hexanols and the like; ethers, such astriethylene or diethylene glycol mono- or di-ethyl ether and the like,as well as mixtures of two or more of these.

The reaction of the phenolic compound with aldehyde or ketone generallytakes place in 0.5 to 8 hours, depending on such factors as the reactiontemperature, amount and nature of alkaline catalyst used, etc. Thecontrol of such factors is well within the skill of the art and theeffect of these factors is apparent. After the reaction has beencompleted to the desired extent, it can be substantially stopped byneutralization of the reaction mixture when an alkaline reagent ispresent. This neutralization can be effected with any suitable acidicmaterial, typically a mineral acid or an organic acid of anhydride; anacidic gas such as carbon dioxide, hydrogen sulfide, sulfur dioxide andthe like, can also be used. Generally neutralization is accomplishedwith a carboxylic acid, especially a lower alkanoic carboxylic acid suchas formic acid, acetic or propionic acid; mixtures of two or more acidscan, of course, be used to accomplish the neutralization. Theneutralization is carried out at a temperature of about 30° to 150° C.An amount of neutralizing agent sufficient to substantially neutralizethe reaction mixture is used. Substantial neutralization means that thereaction mixture is brought to a pH ranging between 4.5 and 8.0. Usuallythe reaction mixture is brought to a minimum pH of about 6 or a maximumpH of about 7.5.

The reaction product, i.e., the phenolic compound, can be recovered fromthe reaction mixture by such techniques as filtration (for example, toremove the product of the neutralization of the alkaline reagent)followed by distillation, evaporation, etc. Such techniques are wellknown to those skilled in the art.

These compositions contain at least one compound which can berepresented by the general formula ##STR11## wherein x, z and g are eachat least one; y' is 0 or at least one, the sum of x, y', z and g doesnot exceed the available valences of Ar; each R' is hydrogen or a "hyd"substituent as described above, and R is as described above.

Often, however, it is not necessary to isolate the phenolic compoundformed from the reaction solvent especially if it is to blended in afuel or lubricant.

When the reaction temperature is in the higher range, i.e., above about100° C., substantial amounts of ether condensation productions can beformed. It is believed that these condensates have the general formula##STR12## wherein q is a number ranging from 2 to about 10. Thesecondensates thus contain alkylene ether linkages, i.e., --CR'₂ O--linkages. Thus, for example, in the case of the reaction of an alkylphenol with formaldehyde, ether condensates are formed having thegeneral formula ##STR13## wherein q is a number ranging from 2 to about10 and R" is an alkyl group of at least 30 carbon atoms. It is possiblethat small amounts of such ether condensates accompany the predominantlylarger uncondensed hydroxy aromatic compounds produced at lowertemperatures.

If a strong acid, such as a mineral acid, is used for theneutralization, it is important to control the amount thereof present soas not to bring the reaction mixture to a low pH than specifiedhereinabove. For example, at lower pH's, over-condensation occurs toform methylene-bridged phenols. The use, however, of carboxylic acidsavoids this problem since they are of sufficiently low acidity they donot promote over-condensation and it is not necessary to regulate soclosely the amount of carboxylic acid used.

The typical phenol or naphthol/formaldehyde-based compounds have thegeneral formula ##STR14## wherein Ar' is a benzene, naphthalene,X-substituted benzene or X-substituted naphthalene nucleus, n is 1 or 2,and R is a hydrocarbon-based substituent of at least about 30 aliphaticcarbon atoms, and X is selected from the group consisting of lower alkylgroups, lower alkoxy groups, lower mercapto groups, fluorine atoms andchlorine atoms. An especially preferred class are those of the generalformula ##STR15## wherein R^(o) is an alkyl substituent of about 30 toabout 300 carbon atoms derived from polymerization orinterpolymerization of at least one monoolefin of 2 to 10 carbon atoms,and m is 1 or 0.

The polynuclear rings of Ar also may be joined by alkylene linkages suchas --CH₂ --. Such methylol substituted phenolic compounds may berepresented by the formula ##STR16## wherein each R is substantiallysaturated hydrocarbon based group of an average of over 10 aliphaticcarbon atoms and preferably over 30 carbon atoms up to about 450 carbonatoms, R' is a lower alkylene group of from one to about 7 carbon atoms,and n is an integer from 0 to 20, preferably 0 to 5.

These linked phenolic compounds can be prepared by reacting the alkylphenols with a slight excess of aldehydes under alkaline conditions tothe presence of a hydrocarbon solvent at reflux temperature. Examples ofsuitable aldehydes include formaldehyde, (formalin or other formaldehydegenerating compound), acetaldehyde, propionaldehyde, butyraldehyde, etc.Formaldehyde is preferred.

When the reaction is completed, the alkali can be washed from thehydrocarbon solution of product, and the product recovered byevaporating or distilling the solvent. Unreacted aldehyde also isremoved in this step.

The alkylated phenols may be any of the alkylated phenolic compoundsdescribed earlier. The preparation of alkylene linked methylolsubstituted phenols is described in the prior art such as in U.S. Pat.No. 3,737,465, which specification is hereby incorporated by referencefor such disclosure.

In another preferred embodiment, the phenols used in the two-cycle oilsof this invention contain one each of the foregoing substituents and buta single aromatic ring, most preferably benzene. This preferred class ofphenols can be represented by the formula ##STR17## wherein the R' groupis a hydrocarbon-based group of about 10 to about 400 aliphatic carbonatoms located ortho or para to the hydroxyl group, R" is a lower alkyl,lower alkoxyl, methylol or lower hydrocarbon based substituted methylolor halogen atom and z is 0 or 1. Usually z is 0 to 2 and R' is asubstantially saturated, purely aliphatic group. Often R' is an alkyl oralkenyl group para to the --OH substituent.

In a still more preferred embodiment of this invention, the phenol is ofthe formula ##STR18## wherein R' is derived from homopolymerized orinterpolymerized C₂₋₁₀ 1-olefins and has an average of from about 30 toabout 300 aliphatic carbon atoms and R" and z are as defined above.Usually R is derived from ethylene, propylene, butylene and mixturesthereof. Typically, it is derived from polymerized isobutene. Often Rhas at least about 50 aliphatic carbon atoms and z is 0.

The following examples describe exemplary preparations of typical alkylphenols for use in the two-cycle engine oils of this invention. As willbe readily apparent to those skilled in the art, alkyl phenols preparedby other techniques can also be used. All parts and percentages are byweight, and all temperatures are in degrees Celsius, in these examplesand elsewhere in this specification unless expressly stated to thecontrary.

EXAMPLE A-1

An alkylated phenol is prepared by reacting phenol with polyisobutenehaving a number average molecular weight of approximately 1000 (vaporphase osmometry) in the presence of a boron trifluoride phenol complexcatalyst. Stripping of the product thus formed first to 230° C./760 torr(vapor temperature) and then to 205° C. vapor temperature/50 torrprovides purified alkylated phenol.

EXAMPLE A-2

The procedure of Example A-1 is repeated except that the polyisobutenehas an average number molecular weight of about 1400.

EXAMPLE A-3

Polyisobutenyl chloride (4885 parts) having a viscosity at 99° C. of1306 SUS and containing 4.7% chlorine is added to a mixture of 1700parts phenol, 118 parts of a sulfuric acid-treated clay and 141 partszinc chloride at 110°-155° C. during a 4-hour period. The mixture isthen kept at 155°-185° C. for 3 hours before being filtered throughdiatomaceous earth. The filtrate is vacuum stripped to 165° C./0.5 torr.The residue is again filtered through diatomaceous earth. The filtrateis a substituted phenol having an OH content of 1.88%.

EXAMPLE A-4

Sodium hydroxide (42 parts of a 20% aqueous sodium hydroxide solution)is added to a mixture of 453 parts of the substituted phenol describedin Example A-3 and 450 parts isopropanol at 30° C. over 0.5 hour.Textile spirits (60 parts) and 112 parts of a 37.7% formalin solutionare added at 20° C. over a 0.8 hour period and the reaction mixture isheld at 4°-25° C. for 92 hours. Additional textile spirits (50 parts),50 parts isopropanol and acetic acid (58 parts of a 50% aqueous aceticacid solution) are added. The pH of the mixture is 5.5 (as determined byASTM procedure D-974). The mixture is dried over 20 parts magnesiumsulfate and then filtered through diatomaceous earth. The filtrate isvacuum stripped to 25° C./10 torr. The residue is the desiredmethylol-substituted product having an OH content of 3.29%.

EXAMPLE A-5

Aluminum chloride (76 parts) is slowly added to a mixture of 4220 partsof polyisobutenyl chloride having a number average molecular weight, Mn,of 1000 (VPO) and containing 4.2% chlorine, 1516 parts phenol, and 2500parts toluene at 60° C. The reaction mixture is kept at 95° C. under abelow-the-surface nitrogen gas purge for 1.5 hours. Hydrochloric acid(50 parts of a 37.5% aqueous hydrochloric acid solution) is added atroom temperature and the mixture stored for 1.5 hours. The mixture iswashed five times with a total of 2500 parts water and then vacuumstripped to 215° C./1 torr. The residue is filtered at 150° C. throughdiatomaceous earth to improve its clarity. The filtrate is a substitutedphenol having an OH content of 1.39%, a Cl content of 0.46% and a Mn of898 (VPO).

EXAMPLE A-6

Paraformaldehyde (38 parts) is added to a mixture of 1399 parts of thesubstituted phenol described in Example A-5, 200 parts toluene, 50 partswater and 2 parts of a 37.5% aqueous hydrochloric acid solution at 50°C. and held for one hour. The mixture is then vacuum stripped to 150°C./15 torr and the residue is filtered through diatomaceous earth. Thefiltrate is the desired product having an OH content of 1.60%, Mn of1688 (GPC) and a weight number average molecular weight, Mw, of 2934(GPC).

EXAMPLE A-7

There are combined and stirred in a reactor having a reflux condenser168 grams (0.19 mole) p-polypropyl phenol of 894 Mn (polypropyl group ofabout 800 Mn), 31 g. formalin (37% CH₂ O) to provide 0.38 moleformaldehyde, 100 ml. hexane and 130 ml. of aqueous 1.5N sodiumhydroxide. The resulting stirred mixture is heated under reflux (about70° C.) for about 16 hours. Thereafter, the resulting mixture is washedthoroughly with water to remove the caustic and the hexane is evaporatedby heating the water washed solution to about 100° C. The residue, aviscous liquid at ambient temperatures contains the bis-methylolcompound of about 4588 Mn having the structure before indicated whereinx is 4 and each R is polypropyl of about 800 Mn.

EXAMPLE A-8

To a reactor having a stirrer and reflux condenser there are added 1070grams of 0.5 gram mole p-polypropylphenol of 900 Mn (polypropyl group ofabout 803 Mn) dissolved (42%) in a mixture of 10 weight percentpolypropylene (803 Mn) and 90 weight percent light mineral oil, 40 gramsNaOH and 200 ml. iso-octane. The resulting solution is stirred andheated while 170 g. of formalin (37% CH₂ O) to provide 2.08 molesformaldehyde are slowly added. The reaction mixture is stirred andheated to 250° F. at which time nitrogen is injected to assist removalof iso-octane. The stirred residue is held at 300° F. for two hours. Theliquid residue is filtered to remove solid NaOH. The filtrate is an oilsolution of the desired product.

Other examples of alkylated phenols useful in accordance with thisinvention are shown in Table A.

                  TABLE A                                                         ______________________________________                                        Example                                                                              Name                    Mol. Wt.                                       ______________________________________                                        A-9    2,2'-dipoly(isobutene)yl-4,4'-                                                                        2500                                                  dihydroxybiphenyl                                                      A-10   8-hydroxy-poly(propene)yl-                                                                             900                                                  1-azanaphthalene                                                       A-11   4-poly(isobutene)yl-1-naphthol                                                                        1700                                           A-12   2-poly(propene/butene-1)yl-                                                                           3200                                                  4,4'-isopropylidene-bisphenol.sup.2                                    A-13   4-tetra(propene)yl-2-hydroxyanthracene                                                                --                                             A-14   4-octadecyl-1,3-dihydroxybenzene                                                                      --                                             A-15   4-poly(isobutene)-3-hydroxypyridine                                                                   1300                                           ______________________________________                                         .sup.1 Number average molecular weight by vapor phase osmometry.              .sup.2 The molar ratio of propene to butene1 in the substituent is 2:3.  

In general, the two-cycle engine lubricating oil compositions of thisinvention contain about 98 to about 55% oil or mixture of oils oflubricating viscosity. Typical compositions contain about 96 to about70% oil. The presently preferred oils are mineral oils and mineraloil-synthetic polymer and/or ester oil mixtures. Polybutenes ofmolecular weights of about 250 to about 1,000 (as measured by vaporphase osmometry) and fatty acid ester oils of polyols such aspentaerythritol and trimethylol propane are typical useful syntheticoils.

These oil compositions may contain about 2 to about 30% and typicallyabout 1 to about 20%, of at least one alkyl phenol as describedhereinabove. Other additives such as auxiliary detergents anddispersents of the ash-producing or ashless type, anti-oxidants,coupling agents, pour point depressing agents, extreme pressure agents,color stabilizers and anti-foam agents can also be present. In apreferred embodiment detergent/dispersants are present in thelubricating compositions of the invention.

(B) The Detergent/Dispersants

In general the detergent/dispersants (B) which may be used in thelubricants of this invention are materials known to those skilled in theart and they have been described in numerous books, articles andpatents. A number of patents are noted hereinbelow in relation tospecific types of detergent/dispersants, and where this is done it is tobe understood that they are incorporated by reference for theirdisclosures relevant to the subject matter discussed at the point in thespecification in which they are identified.

(B)(i) The Neutral or Basic Metal Salts of Organic Sulfur Acids,Carboxylic Acids or Phenols

The choice of metal used to make these salts is usually not critical andtherefore virtually any metal can be used. For reasons of availability,cost and maximum effectiveness, certain metals are more commonly used.These include the metals of Groups I, II and III and in particular thealkali and alkaline earth metals (i.e., the Group IA and IIA metalsexcluding francium and radium). Group IIB metals as well as polyvalentmetals such as aluminum, antimony, arsenic, chromium, molybdenum,wolfram, manganese, iron, cobalt, nickel, and copper can also be used.Salts containing a mixture of ions of two or more of these metals areoften used.

These salts can be neutral or basic. The former contain an amount ofmetal cation just sufficient to neutralize the acidic groups present insalt anion; the latter contain an excess of metal cation and are oftentermed overbased, hyperbased or superbased salts.

These basic and neutral salts can be of oil-soluble organic sulfur acidssuch as sulfonic, sulfamic, thiosulfonic, sulfinic, partial estersulfuric, sulfurous and thiosulfuric acid. Generally they are salts ofcarbocyclic or aliphatic sulfonic acids.

The carbocyclic sulfonic acids include the mono- or poly-nucleararomatic or cycloaliphatic compounds. The oil-soluble sulfonates can berepresented for the most part by the following formulae:

    [R.sub.x --T--(SO.sub.3).sub.y ].sub.z M.sub.b             Formula X

    [R'--(SO.sub.3).sub.a ].sub.d M.sub.b                      Formula XI

In the above formulae, M is either a metal cation as describedhereinabove or hydrogen; T is a cyclic nucleus such as, for example,benzene, naphthalene, anthracene, phenanthrene, diphenylene oxide,thianthrene, phenothioxine, diphenylene sulfide, phenothiazine, diphenyloxide, diphenyl sulfide, diphenylamine, cyclohexane, petroleumnaphthenes, decahydro-naphthalene, cyclopentane, etc; R in Formula X isan aliphatic group such as alkyl, alkenyl, alkoxy, alkoxyalkyl,carboalkoxyalkyl, etc.; x is at least 1, and R_(x) +T contains a totalof at least about 15 carbon atoms. R' in Formula XI is an aliphaticradical containing at least about 15 carbon atoms and M is either ametal cation or hydrogen. Examples of types of the R' radical are alkyl,alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examples of R' aregroups derived from petrolatum, saturated and unsaturated paraffin wax,and polyolefins, including polymerized C₂, C₃, C₄, C₅, C₆, etc., olefinscontaining from about 15 to 7000 or more carbon atoms. The groups T, R,and R' in the above formulae can also contain other inorganic or organicsubstituents in addition to those enumerated above such as, for example,hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide, disulfide,etc. In Formula X, x, y, z and b are at least 1, and likewise in FormulaXI, a, b and d are at least 1.

The following are specific examples of oil-soluble sulfonic acids comingwithin the scope of Formulae X and XI above, and it is to be understoodthat such examples serve also to illustrate the salts of such sulfonicacids useful in this invention. In other words, for every sulfonic acidenumerated it is intended that the corresponding neutral and basic metalsalts thereof are also understood to be illustrated. Such sulfonic acidsare mahogany sulfonic acids; bright stock sulfonic acids; sulfonic acidsderived from lubricating oil fractions having a Saybolt viscosity fromabout 100 seconds at 100° F. to about 200 seconds at 210° F.; petrolatumsulfonic acids; mono- and poly-wax substituted sulfonic and polysulfonicacids of, e.g., benzene, naphthalene, phenol, diphenyl ether,naphthalene disulfide, diphenylamine, thiophene,alpha-chloronaphthalene, etc.; other substituted sulfonic acids such asalkyl benzene sulfonic acids (where the alkyl group has at least 8carbons), cetylphenol mono-sulfide sulfonic acids, dicetyl thianthrenedisulfonic acids, dilauryl beta naphthyl sulfonic acids, dicaprylnetronaphthalene sulfonic acids, and alkaryl sulfonic acids such asdodecyl benzene "bottoms" sulfonic acids.

The latter are acids derived from benzene which has been alkylated withpropylene tetramers or isobutene trimers to introduce 1, 2, 3, or morebranched-chain C₁₂ substituents on the benzene ring. Dodecyl benzenebottoms, principally mixtures of mono- and di-dodecyl benzenes, areavailable as by-products from the manufacture of household detergents.Similar products obtained from alkylation bottoms formed duringmanufacture of linear alkyl sulfonates (LAS) are also useful in makingthe sulfonates used in this invention.

The production of sulfonates from detergent manufacture by-products byreaction with, e.g., so₃, is well known to those skilled in the art.See, for example, the article "Sulfonates" in Kirk-Othmer "Encyclopediaof Chemical Technology", Second Edition, Vol. 19, pp. 291 et seq.published by John Wiley & Sons, N.Y. (1969).

Other descriptions of neutral and basic sulfonate salts and techniquesfor making them can be found in the following U.S. Pat. Nos.: 2,174,110,2,174,506; 2,174,508; 2,193,824; 2,197,800; 2,202,781; 2,212,786;2,213,360; 2,228,598; 2,223,676; 2,239,974; 2,263,312; 2,276,090;2,276,097; 2,315,514; 2,319,121; 2,321,022; 2,333,568; 2,333,788;2,335,259, 2,337,552; 2,347,568, 2,366,027; 2,374,193; 2,383,319;3,312,618; 3,471,403; 3,488,284; 3,595,790; and 3,798,012. These arehereby incorporated by reference for their disclosures in this regard.Also included are aliphatic sulfonic acids such as paraffin wax sulfonicacids, unsaturated paraffin wax sulfonic acids, hydroxy-substitutedparaffin wax sulfonic acids, hexapropylene sulfonic acid, tetra-amylenesulfonic acids, polyisobutene sulfonic acids wherein the polyisobutenecontains from 20 to 7000 or more carbon atoms, chloro-substitutedparaffin wax sulfonic acids, nitro-paraffin wax sulfonic acids, etc;cycloaliphatic sulfonic acids such as petroleum naphthene sulfonicacids, cetyl cyclopentyl sulfonic acids, lauryl cyclohexyl sulfonicacids, bis(di-isobutyl)cyclohexyl sulfonic acids, mono- or poly-waxsubstituted cyclohexyl sulfonic acids, etc.

With respect to the sulfonic acids or salts thereof described herein andin the appended claims, it is intended herein to employ the term"petroleum sulfonic acids" or "petroleum sulfonates" to cover allsulfonic acids or the salts thereof derived from petroleum products. Aparticularly valuable group of petroleum sulfonic acids are the mahoganysulfonic acids (so called because of their reddish-brown color) obtainedas a by-product from the manufacture of petroleum white oils by asulfuric acid process.

Generally Group IA, IIA and IIB neutral and basic salts of theabove-described synthetic and petroleum sulfonic acids are useful in thepractice of this invention.

The carboxylic acids from which suitable neutral and basic salts for usein this invention can be made include aliphatic, cycloaliphatic, andaromatic mono- and polybasic carboxylic acids such as the naphthenicacids, alkyl- or alkenyl-substituted cyclopentanoic acids, alkyl- oralkenyl-substituted cyclohexanoic acids, alkyl- or alkenyl-substitutedaromatic carboxylic acids. The aliphatic acids generally contain atleast eight carbon atoms and preferably at least twelve carbon atoms.Usually they have no more than about 400 carbon atoms. Generally, if thealiphatic carbon chain is branched, the acids are more oil-soluble forany given carbon atoms content. The cycloaliphatic and aliphaticcarboxylic acids can be saturated or unsaturated. Specific examplesinclude 2-ethylhexanoic acids, alpha-linolenic acid,propylene-tetramer-substituted maleic acid, behenic acid, isostearicacid, pelargonic acid, capric acid, palmitoleic acid, linoleic acid,lauric acid, oleic acid, ricinoleic acid, undecylic acid,dioctylcyclopentane carboxylic acid, myristic acid,dilauryldecahydronaphthalene carboxylic acid, stearyl-octahydroindenecarboxylic acid, palmitic acid, commercially available mixtures of twoor more carboxylic acids such as tall oil acids, rosin acids, and thelike.

A preferred group of oil-soluble carboxylic acids useful in preparingthe salts used in the present invention are the oil-soluble aromaticcarboxylic acids. These acids are represented by the general formula:##STR19## where R* is an aliphatic hydrocarbon-based group of at leastfour carbon atoms, and no more than about 400 aliphatic carbon atoms, ais an integer of from one to four, Ar* is a polyvalent aromatichydrocarbon nucleus of up to about 14 carbon atoms, each X isindependently a sulfur or oxygen atoms, and m is an integer of from oneto four with the proviso that R* and a are such that there is an averageof at least 8 aliphatic carbon atoms provided by the R* groups of eachacid molecule represented by Formula XII. Examples of aromatic nucleirepresented by the variable Ar* are the polyvalent aromatic radicalsderived from benzene, naphthalene, anthracene, phenanthrene, indene,fluorene, biphenyl, and the like. Generally, the radical represented byAr* will be a polyvalent nucleus derived from benzene or naphthalenesuch as phenylenes and naphthylene, e.g., methylphenylenes,ethoxyphenylenes, nitrophenylenes, isopropylphenylenes,hydroxyphenylenes, mercaptophenylenes, N,N-dimethylaminophenylenes,chlorophenylenes, dipropoxynaphthylenes, triethylnaphthylenes, andsimilar tri-, tetra-, pentavalent nuclei thereof, etc.

The R* groups are usually purely hydrocarbyl groups, preferably groupssuch as alkyl or alkenyl radicals. However, the R* groups can containsmall number substituents such as phenyl, cycloalkyl (e.g., cyclohexyl,cyclopentyl, etc.) and nonhydrocarbon groups such as nitro, amino, halo(e.g., chloro, bromo, etc.), lower alkoxy, lower alkyl mercapto, oxosubstituents (i.e., ═O), thio groups (i.e., ═S), interrupting groupssuch as --NH--, --O--, --S--, and the like provided the essentiallyhydrocarbon character of the R* group is retained. The hydrocarboncharacter is retained for purposes of this invention so long as anynon-carbon atoms present in the R* groups do not account for more thanabout 10% of the total weight of the R* groups.

Examples of R* groups include butyl, isobutyl, pentyl, octyl, nonyl,dodecyl, docosyl, tetracontyl, 5-chlorohexyl, 4-ethoxypentyl, 2-hexenyl,e-cyclohexyloctyl, 4-(p-chlorophenyl)-octyl, 2,3,5-trimethylheptyl,2-ethyl-5-methyloctyl, and substituents derived from polymerized olefinssuch as polychloroprenes, polyethylenes, polypropylenes,polyisobutylenes, ethylene-propylene copolymers, chlorinated olefinpolymers, oxidized ethylene-propylene copolymers, and the like.Likewise, the group Ar may contain non-hydrocarbon substituents, forexample, such diverse substituents as lower alkoxy, lower alkylmercapto, nitro, halo, alkyl or alkenyl groups of less than four carbonatoms, hydroxy, mercapto, and the like.

A group of particularly useful carboxylic acids are those of theformula: ##STR20## where R*, X, Ar*, m and a are as defined in FormulaXIV and p is an integer of 1 to 4, usually 1 or 2. Within this group, anespecially preferred class of oil-soluble carboxylic acids are those ofthe formula: ##STR21## where R** in Formula XIV is an aliphatichydrocarbon group containing at least 4 to about 400 carbon atoms, a isan integer of from 1 to 3, b is 1 or 2, c is zero, 1, or 2 andpreferably 1 with the proviso that R** and a are such that the acidmolecules contain at least an average of about twelve aliphatic carbonatoms in the aliphatic hydrocarbon substituents per acid molecule. Andwithin this latter group of oil-soluble carboxylic acids, thealiphatic-hydrocarbon substituted salicyclic acids wherein eachaliphatic hydrocarbon substituent contains an average of at least aboutsixteen carbon atoms per substituent and one to three substituents permolecule are particularly useful. Salts prepared from such salicyclicacids wherein the aliphatic hydrocarbon substituents are derived frompolymerized olefins, particularly polymerized lower 1-mono-olefins suchas polyethylene, polypropylene, polyisobutylene, ethylene/propylenecopolymers and the like and having average carbon contents of about 30to 400 carbon atoms.

The carboxylic acids corresponding to Formulae XII and XIII above arewell known or can be prepared according to procedures known in the art.Carboxylic acids of the type illustrated by the above formulae andprocesses for preparing their neutral and basic metal salts are wellknown and disclosed, for example, in such U.S. Pat. Nos. as 2,197,832;2,197,835; 2,252,662; 2,252,664; 2,714,092; 3,410,798 and 3,595,791.

Another type of neutral and basic carboxylate salt used in thisinvention are those derived from alkenyl succinates of the generalformula ##STR22## wherein R* is as defined above in Formula XII. Suchsalts and means for making them are set forth in U.S. Pat. Nos.3,271,130; 3,567,637 and 3,632,610, which are hereby incorporated byreference in this regard.

Other patents specifically describing techniques for making basic saltsof the hereinabove-described sulfonic acids, carboxylic acids, andmixtures of any two or more of these include U.S. Pat. Nos. 2,501,731;2,616,904; 2,616,905; 2,616,906; 2,616,911, 2,616,924; 2,616,925;2,617,049, 2,777,874; 3,027,325; 3,256,186; 3,282,835; 3,384,585;3,373,108; 3,368,396; 3,342,733; 3,320,162; 3,312,618; 3,318,809;3,471,403; 3,488,284; 3,595,790; and 3,629,109. The disclosures of thesepatents are hereby incorporated in this present specification for theirdisclosure in this regard as well as for their disclosure of specificsuitable basic metal salts.

Neutral and basic salts of phenols (generally known as phenates) arealso useful in the compositions of this invention and well known tothose skilled in the art. The phenols from which these phenates areformed are of the general formula

    (R*).sub.n --(Ar*)--(XH).sub.m                             Formula XVI

wherein R*, n, Ar*, X and m have the same meaning and preferences asdescribed hereinabove with reference to Formula XII. The same examplesdescribed with respect to Formula XII also apply.

The commonly available class of phenates are those made from phenols ofthe general formula ##STR23## wherein a is an integer of 1-3, b is of 1or 2, z is 0 or 1, R' in Formula XVII is a substantially saturatedhydrocarbon-based substituent having an average of from 30 to about 400aliphatic carbon atoms and R is selected from the group consisting oflower alkyl, lower alkoxyl, nitro, and halo groups.

One particular class of phenates for use in this invention are the basic(i.e., overbased, etc.) Group IIA metal sulfurized phenates made bysulfurizing a phenol as described hereinabove with a sulfurizing agentsuch as sulfur, a sulfur halide, or sulfide or hydrosulfide salt.Techniques for making these sulfurized phenates are described in U.S.Pat. Nos. 2,680,096; 3,036,971 and 3,775,321 which are herebyincorporated by reference for their disclosures in this regard.

Other phenates that are useful are those that are made from phenols thathave been linked through alkylene (e.g., methylene) bridges. These aremade by reacting single or multi-ring phenols with aldehydes or ketones,typically, in the presence of an acid or basic catalyst. Such linkedphenates as well as sulfurized phenates are described in detail in U.S.Pat. No. 3,350,038; particularly columns 6-8 thereof, which is herebyincorporated by reference for its disclosures in this regard.

Naturally, mixtures of two or more neutral and basic salts of thehereinabove described organic sulfur acids, carboxylic acids and phenolscan be used in the compositions of this invention. Usually the neutraland basic salts will be sodium, lithium, magnesium, calcium, or bariumsalts including mixtures of two or more of any of these.

(B)(ii) The Hydrocarbyl-Substituted Amine

The hydrocarbyl-substituted amines used in making the compositions ofthis invention are well known to those of skill in the art and they aredescribed in a number of patents. Among these are U.S. Pat. Nos.3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; and 3,822,209.These patents are hereby incorporated by their reference for theirdisclosure of suitable hydrocarbyl amines for use in the presentinvention including their method of preparation.

A typical hydrocarbyl amine has the general formula: ##STR24## wherein Ais hydrogen, a hydrocarbyl group of from 1 to 10 carbon atoms, orhydroxyhydrocarbyl group of from 1 to 10 carbon atoms; X is hydrogen, ahydrocarbyl group of from 1 to 10 carbon atoms, or hydroxyhydrocarbylgroup of from 1 to 10 carbon atoms, and may be taken together with A andN to form a ring of from 5 to 6 annular members and up to 12 carbonatoms; U is an alkylene group of from 2 to 10 carbon atoms, R² is analiphatic hydrocarbon of from about 30 to 400 carbon atoms; a is aninteger of from 0 to 10; b is an integer of from 0 to 1; a+2b is aninteger of from 1 to 10; c is an integer of from 1 to 5 and is as anaverage in the range of 1 to 4, and equal to or less than the number ofnitrogen atoms in the molecule; x is an integer of from 0 to 1; y is aninteger of from 0 to 1; and x+y is equal to 1.

In interpreting this formula, it is to be understood that the R² and Hatoms are attached to the unsatisfied nitrogen valences within thebrackets of the formula. Thus, for example, the formula includessubgeneric formulae wherein the R² is attached to terminal nitrogens andisomeric subgeneric formula wherein it is attached to non-terminalnitrogen atoms. Nitrogen atoms not attached to an R² may bear a hydrogenor an AXN substituent.

The hydrocarbyl amines useful in this invention and embraced by theabove formula include monoamines of the general formula

    AXNR.sup.2                                                 Formula XIX

Illustrative of such monoamines are the following:

poly(propylene)amine

N,N-dimethyl-N-poly(ethylene/propylene)amine (50:50 mole ratio ofmonomers)

poly(isobutene)amine

N,N-di(hydroxyethyl)-N-poly(isobutene)amine

poly(isobutene/1-butene/2-butene)amine (50:25:25 mole ratio of monomer)

N-(2-hydroxypropyl)-N-poly(isobutene)amine

N-poly(1-butene)-aniline

N-poly(isobutene)-morpholine

Among the hydrocarbyl amines embraced by the general Formula XVII as setforth above, are polyamines of the general formula ##STR25##Illustrative of such polyamines are the following:N-poly(isobutene)ethylene diamine

N-poly(propylene)trimethylene diamine

N-poly(1-butene)diethylene triamine

N',N'-poly(isobutene)tetraethylene pentamine

N,N-dimethyl-N'-poly(propylene), 1,3-propylene diamine

The hydrocarbyl substituted amines useful in forming the compositions ofthis invention include certain N-amino-hydrocarbyl morpholines which arenot embraced in the general Formula XVIII above. Thesehydrocarbyl-substituted aminohydrocarbyl morpholines have the generalformula: ##STR26## wherein R² is an aliphatic hydrocarbon group of fromabout 30 to about 400 carbons, A is hydrogen, hydrocarbyl of from 1 to10 carbon atoms or hydroxy hydrocarbyl group of from 1 to 10 carbonatoms and U is an alkylene group of from 2 to 10 carbon atoms. Thesehydrocarbyl-substituted aminohydrocarbyl morpholines as well as thepolyamines described by Formula XIX are among the typicalhydrocarbyl-substituted amines used in preparing compositions of thisinvention.

(B)(iii) The acylated Nitrogen-Containing Compounds

A number of acylated, nitrogen-containing compounds having a substituentof at least 10 aliphatic carbon atoms and made by reacting a carboxylicacid acylating agent with an amino compound are known to those skilledin the art. In such compositions the acylating agent is linked to theamino compound through an imido, amido, amidine or acyloxy ammoniumlinkage. The substituent of 10 aliphatic carbon atoms may be in eitherthe carboxylic acid acylating agent derived portion of the molecule orin the amino compound derived portion of the molecule. Preferably,however, it is in the acylating agent portion. The acylating agent canvary from formic acid and its acylating derivatives to acylating agentshaving high molecular weight aliphatic substituents of up to 5,000,10,000 or 20,000 carbon atoms. The amino compounds can vary from ammoniaitself to amines having aliphatic substituents of up to about 30 carbonatoms.

A typical class of acylated amino compounds useful in making thecompositions of this invention are those made by reacting an acylatingagent having an aliphatic substituent of at least 10 carbon atoms and anitrogen compound characterized by the presence of at least one --NHgroup. Typically, the acylating agent will be a mono- or polycarboxylicacid (or reactive equivalent thereof) such as a substituted succinic orpropionic acid and the amino compound will be a polyamine or mixture ofpolyamines, most typically, a mixture of ethylene polyamines. Thealiphatic substituent in such acylating agents is often of at leastabout 50 and up to about 400 carbon atoms. Usually it belongs to thesame generic class as the R' group of the phenols (A) and therefore thepreferences, examples and limitation discussed hereinabove relating toR' apply equally to this aliphatic substituent. Exemplary of aminocompounds useful in making these acylated compounds are the following:

(1) polyalkylene polyamines of the general formula ##STR27## whereineach R''' is independently a hydrogen atom or a C₁₋₁₂ hydrocarbon-basedgroup, with proviso that at least one R is a hydrogen atom, n is a wholenumber of 1 to 10 and U is a C₂₋₁₀ alkylene group, (2)heterocyclic-substituted polyamines of the formula ##STR28## whereinR''' and U are as defined hereinabove, m is 0 or a whole number of 1 to10, m' is a whole number of 1 to 10 and Y is oxygen or divalent sulfuratom or a N--R''' group and (3) aromatic polyamines of the generalformula

    Ar(NR'''.sub.2).sub.y                                      Formula XXIV

wherein Ar is an aromatic nucleus of 6 to about 20 carbon atoms, eachR''' is as defined hereinabove and y is 2 to about 8. Specific examplesof the polyalkylene polyamines (1) are ethylene diamine,tetra(ethylene)pentamine, tri-(trimethylene)tetramine, 1,2-propylenediamine, etc. Specific examples of the heterocyclic-substitutedpolyamines (2) are N-2-aminoethyl piperazine, N-2 and N-3 amino propylmorpholine, N-3-(dimethyl amino)propyl piperazine, etc. Specificexamples of the aromatic polyamines (3) are the various isomericphenylene diamines, the various isomeric naphthalene diamines, etc.

Many patents have described useful acylated nitrogen compounds includingU.S. Pat. Nos. 3,172,892; 3,219,666; 3,272,746; 3,310,492; 3,341,542;3,444,170; 3,455,831; 3,455,832; 3,576,743; 3,630,904; 3,632,511; and3,804,763. A typical acylated nitrogen-containing compound of this classis that made by reacting a poly(isobutene)-substituted succinicanhydride acylating agent (e.g., anhydride, acid, ester, etc.) whereinthe poly(isobutene) substituent has between about 50 to about 400 carbonatoms with a mixture of ethylene polyamines having 3 to about 7 aminonitrogen atoms per ethylene polyamine and about 1 to about 6 ethyleneunits made from condensation of ammonia with ethylene chloride. In viewof the extensive disclosure of this type of acylated amino compound,further discussion of their nature and method of preparation is notneeded here. Instead, the above-noted U.S. Patents are herebyincorporated by reference for their disclosure of acylated aminocompounds and their method of preparation.

Another type of acylated nitrogen compound belonging to this class isthat made by reacting the afore-described alkylene amines with theafore-described substituted succinic acids or anhydrides and aliphaticmonocarboxylic acids having from 2 to about 22 carbon atoms. In thesetypes of acylated nitrogen compounds, the mole ratio of succinic acid tomonocarboxylic acid ranges from about 1:0.1 to about 1:1. Typical of themonocarboxylic acid are formic acid, acetic acid, dodecanoic acid,butanoic acid, oleic acid, stearic acid, the commercial mixture ofstearic acid isomers known as isostearic acid, tolyl acid, etc. Suchmaterials are more fully described in U.S. Pat. Nos. 3,216,936 and3,250,715 which are hereby incorporated by reference for theirdisclosures in this regard.

Still another type of acylated nitrogen compound useful in making thecompositions of this invention is the product of the reaction of a fattymonocarboxylic acid of about 12-30 carbon atoms and the aforedescribedalkylene amines, typically, ethylene, propylene or trimethylenepolyamines containing 2 to 8 amino groups and mixtures thereof. Thefatty monocarboxylic acids are generally mixtures of straight andbranched chain fatty carboxylic acids containing 12-30 carbon atoms. Awidely used type of acylated nitrogen compound is made by reacting theafore-described alkylene polyamines with a mixture of fatty acids havingfrom 5 to about 30 mole percent straight chain acid and about 70 toabout 95 percent mole branched chain fatty acids. Among the commerciallyavailable mixtures are those known widely in the trade as isostearicacid. These mixtures are produced as a by-product from the dimerizationof unsaturated fatty acids as described in U.S. Pat. Nos. 2,812,342 and3,260,671.

The branched chain fatty acids can also include those in which thebranch is not alkyl in nature, such as found in phenyl and cyclohexylstearic acid and the chloro-stearic acids. Branched chain fattycarboxylic acid/alkylene polyamine products have been describedextensively in the art. See for example, U.S. Pat. Nos. 3,110,673;3,251,853; 3,326,801; 3,337,459; 3,405,064; 3,429,674; 3,468,639;3,857,791. These patents are hereby incorporated by reference for theirdisclosure of fatty acid/polyamine condensates for their use inlubricating oil formulations.

(B)(iv) The Nitrogen-containing Condensates of Phenols, Aldehydes, andAmino Compounds

The phenol/aldehyde/amino compound condensates useful in making thedetergent/dispersants of this invention include those genericallyreferred to as Mannich condensates. Generally they are made by reactingsimultaneously or sequentially at least one active hydrogen compoundsuch as a hydrocarbon-substituted phenol (e.g., and alkyl phenol whereinthe alkyl group has at least about 30 up to about 400 carbon atoms),having at least one hydrogen atom bonded to an aromatic carbon, with atleast one aldehyde or aldehyde-producing material (typicallyformaldehyde or formaldehyde precursor) and at least one amino orpolyamino compound having at least one NH group. The amino compoundsinclude primary or secondary monoamines having hydrocarbon substituentsof 1 to 30 carbon atoms or hydroxyl-substituted hydrocarbon substituentsof 1 to about 30 carbon atoms. Another type of typical amino compoundare the polyamines described during the discussion of the acylatednitrogen-containing compounds.

Exemplary mono-amines include methyl ethyl amine, methyl octadecylamine, aniline, diethyl amine, diethanol amine, dipropyl amine and soforth. The following U.S. Patents contain extensive descriptions ofMannich condensates which can be used in making the compositions of thisinvention:

    ______________________________________                                        U.S. PAT. Nos.                                                                ______________________________________                                        2,459,112      3,413,347    3,558,743                                         2,962,442      3,442,808    3,586,629                                         2,984,550      3,448,047    3,591,598                                         3,036,003      3,454,497    3,600,372                                         3,166,516      3,459,661    3,634,515                                         3,236,770      3,461,172    3,649,229                                         3,355,270      3,493,520    3,697,574                                         3,368,972      3,539,633                                                      ______________________________________                                    

These patents are hereby incorporated by reference for their disclosuresrelating to the production and use of Mannich condensate products inlubricant compositions.

Condensates made from sulfur-containing reactants also can be used inthe compositions of the present invention. Such sulfur-containingcondensates are described in U.S. Pat. Nos. 3,368,972; 3,649,229;3,600,372; 3,649,659; and 3,741,896. These patents are also incorporatedby reference for their disclosure of sulfur-containing Mannichcondensates. Generally the condensates used in making compositions ofthis invention are made from a phenol bearing an alkyl substituent ofabout 6 to about 400 carbon atoms, more typically, 30 to about 250carbon atoms. These typical condensates are made from formaldehyde orC₂₋₇ aliphatic aldehyde and an amino compound such as those used inmaking the acylated nitrogen-containing compounds described under(B)(iii).

These preferred condensates are prepared by reacting about one molarportion of phenolic compound with about 1 to about 2 molar portions ofaldehyde and about 1 to about 5 equivalent portions of amino compound(an equivalent of amino compound is its molecular weight divided by thenumber of ═NH groups present). The conditions under which suchcondensation reactions are carried out are well known to those skilledin the art as evidenced by the above-noted patents. Therefore, thesepatents are also incorporated by reference for their disclosuresrelating to reaction conditions.

A particularly preferred class of condensation products for use in thepresent invention are those made by a "2-step process" as disclosed incommonly assigned U.S. Ser. No. 451,644, filed Mar. 15, 1974 nowabandoned. Briefly, these nitrogen-containing condensates are made by(1) reacting at least one hydroxy aromatic compound containing analiphatic-based or cycloaliphatic-based substituent which has at leastabout 30 carbon atoms and up to about 400 carbon atoms with a loweraliphatic C_(k-7) aldehyde or reversible polymer thereof in the presenceof an alkaline reagent, such as an alkali metal hydroxide, at atemperature up to about 150° C.; (2) substantially neutralizing theintermediate reaction mixture thus formed; and (3) reacting theneutralized intermediate with at least one compound which contains anamino group having at least one --NH-- group.

More preferably, these 2-step condensates are made from (a) phenolsbearing a hydrocarbon-based substituent having about 30 to about 250carbon atoms, said substituent being derived from a polymer ofpropylene, 1-butene, 2-butene, or isobutene and (b) formaldehyde, orreversible polymer thereof, (e.g., trioxane, paraformaldehyde) orfunctional equivalent thereof, (e.g., methylol) and (c) an alkylenepolyamine such as ethylene polyamines having between 2 and 10 nitrogenatoms. Further details as to this preferred class of condensates can befound in the hereinabove noted U.S. Ser. No. 451,644, which is herebyincorporated by reference, for its disclosures relating to 2-stepcondensates.

(B)(v) The Esters of Substituted Polycarboxylic Acids

The ester useful as detergents/dispersants in this invention arederivatives of substituted carboxylic acids in which the substituent isa substantially aliphatic, substantially saturated hydrocarbon-basedradical containing at least about 30 (preferably about 50 to about 750)aliphatic carbon atoms. As used herein, the term "hydrocarbon-basedradical" denotes a radical having a carbon atom directly attached to theremainder of the molecule and having predominantly hydrocarbon characterwithin the context of this invention. Such radicals include thefollowing:

(1) Hydrocarbon radicals; that is, aliphatic radicals, aromatic- andalicyclic-substituted aliphatic radicals, and the like, of the typeknown to those skilled in the art.

(2) Substituted hydrocarbon radicals; that is, radicals containingnon-hydrocarbon substituents which, in the context of this invention, donot alter the predominantly hydrocarbon character of the radical. Thoseskilled in the art will be aware of suitable substituents; examples arehalo, nitro, hydroxy, alkoxy, carbalkoxy and alkylthio.

(3) Hetero radicals; that is, radicals which, while predominantlyhydrocarbon in character within the context of this invention, containatoms other than carbon present in a chain or ring otherwise composed ofcarbon atoms. Suitable hetero atoms will be apparent to those skilled inthe art and include, for example, nitrogen, oxygen and sulfur.

In general, no more than about three substituents or hetero atoms, andpreferably no more than one, will be present for each 10 carbon atoms inthe hydrocarbon-based radical.

The substituted carboxylic acids (and derivatives thereof includingesters, amides and imides) are normally prepared by the alkylation of anunsaturated acid, or a derivative thereof such as an anhydride, ester,amide or imide, with a source of the desired hydrocarbon-based radical.Suitable unsaturated acids and derivatives thereof include acrylic acid,methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconicacid, itaconic anhydride, citraconic acid, citraconic anhydride,mesaconic acid, glutaconic acid, chloromaleic acid, aconitic acid,crotonic acid, methylcrotonic acid, sorbic acid, 3-hexenoic acid,10-decenoic acid and 2-pentene-1,3,5-tricarboxylic acid. Particularlypreferred are the unsaturated dicarboxylic acids and their derivatives,especially maleic acid, fumaric acid and maleic anhydride.

Suitable alkylating agents include homopolymers and interpolymers ofpolymerizable olefin monomers containing from about 2 to about 10 andusually from about 2 to about 6 carbon atoms, and polarsubstituent-containing derivatives thereof. Such polymers aresubstantially saturated (i.e., they contain no more than about 5%olefinic linkages) and substantially aliphatic (i.e., they contain atleast about 80% and preferably at least about 95% by weight of unitsderived from aliphatic monoolefins). Illustrative monomers which may beused to produce such polymers are ethylene, propylene, 1-butene,2-butene, isobutene, 1-octene and 1-decene. Any unsaturated units may bederived from conjugated dienes such as 1,3-butadiene and isoprene;non-conjugated dienes such as 1,4-hexadiene, 1,4-cyclohexadiene,5-ethylidene-2-norbornene and 1,6-octadiene; and trienes such as1-isopropylidene-3a,4,7,-7a-tetrahydroindene,1-isopropylidenedicyclopentadiene and2-(2-methylene-4-methyl-3-pentenyl) [2.2.1]bicyclo-5-heptene.

A first preferred class of polymers comprises those of terminal olefinssuch as propylene, 1-butene, isobutene and 1-hexene. Especiallypreferred within this class are polybutenes comprising predominantlyisobutene units. A second preferred class comprises terpolymers ofethylene, a C₃₋₈ alpha-monoolefin and a polyene selected from the groupconsisting of non-conjugated dienes (which are especially preferred) andtrienes. Illustrative of these terpolymers is "Ortholeum 2052"manufactured by E. I. duPont de Nemours & Company, which is a terpolymercontaining about 48 mole percent ethylene groups, 48 mole percentpropylene groups and 4 mole percent 1,4-hexadiene groups and having aninherent viscosity of 1.35 (8.2 grams of polymer in 100 ml. of carbontetrachloride at 30° C.).

Methods for the preparation of the substituted carboxylic acids andderivatives thereof are well known in the art and need not be describedin detail. Reference is made, for example, to U.S. Pat. Nos. 3,272,746;3,522,179; and 4,234,435, which are incorporated by reference herein.The mole ratio of the polymer to the unsaturated acid or derivativethereof may be equal to, greater than or less than 1, depending on thetype of product desired.

When the unsaturated acid or derivative thereof is maleic acid, fumaricacid or maleic anhydride, the alkylation product is a substitutedsuccinic acid or derivative thereof. These substituted succinic acidsand derivatives are particularly preferred for preparing thecompositions of this invention.

The esters are those of the above-described succinic acids with hydroxycompounds which may be aliphatic compounds such as monohydric andpolyhydric alcohols or aromatic compounds such as phenols and naphthols.The aromatic hydroxy compounds from which the esters of this inventionmay be derived are illustrated by the following specific examples:phenol, beta-naphthol, alpha-naphthol, cresol, resorcinol, catechol,p,p'dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, propenetetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-phenol,alpha-decyl-beta-naphthol, polyisobutene(molecular weight of1000)-substituted phenol, the condensation product of heptylphenol with0.5 mole of formaldehyde, the condensation product of octylphenol withacetone, di(hydroxyphenyl)oxide, di(hydroxyphenyl)sulfide,di(hydroxyphenyl)disulfide, and 4-cyclohexylphenol. Phenol and alkylatedphenols having up to three alkyl substituents are preferred. Each of thealkyl substituents may contain 100 or more carbon atoms.

The alcohols from which the esters may be derived preferably contain upto about 40 aliphatic carbon atoms. They may be monohydric alcohols suchas methanols, ethanol, isooctanol, dodecanol, cyclohexanol,cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol,isobutyl alcohol, benzyl alcohol, beta-phenylethyl alcohol,2-methylcyclohexanol, beta-chloroethanol, monomethyl ether of ethyleneglycol, monobutyl ether of ethylene glycol, monopropyl ether ofdiethylene glycol, monododecyl ether of triethylene glycol, mono-oleateof ethylene glycol, monostearate of diethylene glycol, sec-pentylalcohol, tert-butyl alcohol, 5-bromo-dodecanol, nitro-octadecanol anddioleate of glycerol. The polyhydric alcohols preferably contain from 2to about 10 hydroxy radicals. They are illustrated by, for example,ethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, dipropylene glycol, tripropylene glycol, dibutylene glycol,tributylene glycol, and other alkylene glycols in which the alkyleneradical contains from 2 to about 8 carbon atoms. Other useful polyhydricalcohols include glycerol, mono-oleate of glycerol, mono-stearate ofglycerol, monomethyl ether of glycerol, pentaerythritol, 9,10-dihydroxystearic acid, methyl ester of 9,10-dihydroxy stearic acid,1,2-butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol,arabitol, sorbitol, mannitol, 1,2-cyclohexanediol, and xylene glycol.Carbohydrates such as sugars, starches, celluloses, etc., likewise mayyield the esters of this invention. The carbohydrates may be exemplifiedby a glucose, fructose, sucrose, rhamnose, mannose, glyceraldehyde, andgalactose.

An especially preferred class of polyhydric alcohols are those having atleast three hydroxy radicals, some of which have been esterified with amonocarboxylic acid having from about 8 to about 30 carbon atoms such asoctanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid,or tall oil acid. Examples of such partially esterified polyhydricalcohols are the mono-oleate of sorbitol, distearate of sorbitol,mono-oleate of glycerol, monostearate of glycerol, di-dodecanoate oferythritol.

The esters may also be derived from unsaturated alcohols such as allylalcohol, cinnamyl alcohol, propargyl alcohol, 1-cyclohexene-3-ol, anoleyl alcohol. Still other classes of the alcohols capable of yieldingthe esters of this invention comprise the ether-alcohols andamino-alcohols including, for example, the oxyalkylene-, oxy-arylene-,amino-alkylene-, and amino-arylene-substituted alcohols having one ormore oxy-alkylene, amino-alkylene or amino-arylene oxy-arylene radicals.They are exemplified by Cellosolve, carbitol, phenoxy-ethanol,heptylphenyl-(oxypropylene)₆ -H, octyl-(oxyethylene)₃₀ -H,phenyl-(oxyoctylene)₂ -H, mono(heptylphenyloxypropylene)-substitutedglycerol, poly(styrene oxide), amino-ethanol, 3-amino ethyl-pentanol,di(hydroxyethyl)amine, p-aminophenol, tri(hydroxypropyl)amine,N-hydroxyethyl ethylene diamine, N,N,N',N'-tetrahydroxytrimethylenediamine, and the like. For the most part, the ether-alcohols having upto about 150 oxy-alkylene radicals in which the alkylene radicalcontains from 1 to about 8 carbon atoms are preferred.

The esters may be di-esters of succinic acids or acidic esters, i.e.,partially esterified succinic acids; as well as partially esterifiedpolyhydric alcohols or phenols, i.e., esters having free alcoholic orphenolic hydroxyl radicals. Mixtures of the above-illustrated esterslikewise are contemplated within the scope of the invention.

The esters may be prepared by one of several methods. The method whichis preferred because of convenience and superior properties of theesters it produces, involves the reaction of a suitable alcohol orphenol with a substantially hydrocarbon-substituted succinic anhydride.The esterification is usually carried out at a temperature above about100° C., preferably between 150° C. and 300° C.

The water formed as a by-product is removed by distillation as theesterification proceeds. A solvent may be used in the esterification tofacilitate mixing and temperature control. It also facilitates theremoval of water from the reaction mixture. The useful solvents includexylene, toluene, diphenyl ether, chlorobenzene, and mineral oil.

A modification of the above process involves the replacement of thesubstituted succinic anhydride with the corresponding succinic acid.However, succinic acids readily undergo dehydration at temperaturesabove about 100° C. and are thus converted to their anhydrides which arethen esterified by the reaction with the alcohol reactant. In thisregard, succinic acids appear to be the substantial equivalent of theiranhydrides in the process.

The relative proportions of the succinic reactant and the hydroxyreactant which are to be used depend to a large measure upon the type ofthe product desired and the number of hydroxyl groups present in themolecule of the hydroxy reactant. For instance, the formation of a halfester of a succinic acid, i.e., one in which only one of the two acidradicals is esterified, involves the use of one mole of a monohydricalcohol for each mole of the substituted succinic acid reactant, whereasthe formation of a diester of a succinic acid involves the use of twomoles of the alcohol for each mole of the acid. On the other hand, onemole of a hexahydric alcohol may combine with as many as six moles of asuccinic acid to form an ester in which each of the six hydroxylradicals of the alcohol is esterified with one of the two acid radicalsof the succinic acid. Thus, the maximum proportion of the succinic acidto be used with a polyhydric alcohol is determined by the number ofhydroxyl groups present in the molecule of the hydroxy reactant. For thepurposes of this invention, it has been found that esters obtained bythe reaction of equi-molar amounts of the succinic acid reactant andhydroxy reactant have superior properties and are therefore preferred.

In some instances it is advantageous to carry out the esterification inthe presence of a catalyst such as sulfuric acid, pyridinehydrochloride, hydrochloric acid, benzene sulfonic acid, p-toluenesulfonic acid, phosphoric acid, or any other known esterificationcatalyst. The amount of the catalyst in the reaction may be as little as0.01% (by weight of the reaction mixture), more often from about 0.1% toabout 5%.

The esters of this invention likewise may be obtained by the reaction ofa substituted succinic acid or anhydride with an epoxide or a mixture ofan epoxide and water. Such reaction is similar to one involving the acidor anhydride with a glycol. For instance, the product may be prepared bythe reaction of a substituted succinic acid with one mole of ethyleneoxide. Similarly, the product may be obtained by the reaction of asubstituted succinic acid with two moles of ethylene oxide. Otherepoxides which are commonly available for use in such reaction include,for example, propylene oxide, styrene oxide, 1,2-butylene oxide,2,3-butylene oxide, epichlorohydrin, cyclohexene oxide, 1,2-octyleneoxide, epoxidized soya bean oil, methyl ester of 9,10-epoxy-stearicacid, and butadiene mono-epoxide. For the most part, the epoxides arethe alkylene oxides in which the alkylene radical has from 2 to about 8carbon atoms; or the epoxidized fatty acid esters in which the fattyacid radical has up to about 30 carbon atoms and the ester radical isderived from a lower alcohol having up to about 8 carbon atoms.

In lieu of the succinic acid or anhydride, a substituted succinic acidhalide may be used in the processes illustrated above for preparing theesters of this invention. Such acid halides may be acid dibromides, aciddichlorides, acid monochlorides, and acid monobromides. The substitutedsuccinic anhydrides and acids can be prepared by, for example, thereaction of maleic anhydride with a high molecular weight olefin or ahalogenated hydrocarbon such as is obtained by the chlorination of anolefin polymer described previously. The reaction involves merelyheating the reactants at a temperature preferably from about 100° C. toabout 250° C. The product from such a reaction is an alkenyl succinicanhydride. The alkenyl group may be hydrogenated to an alkyl group. Theanhydride may be hydrolyzed by treatment with water or steam to thecorresponding acid. Another method useful for preparing the succinicacids or anhydrides involves the reaction of itaconic acid or anhydridewith an olefin or a chlorinated hydrocarbon at a temperature usuallywithin the range from about 100° C. to about 250° C. The succinic acidhalides can be prepared by the reaction of the acids or their anhydrideswith a halogenation agent such as phosphorus tribromide, phosphoruspentachloride, or thionyl chloride. These and other methods of preparingthe succinic compounds are well known in the art and need not beillustrated in further detail here.

Still other methods of preparing the esters of this invention areavailable. For instance, the esters may be obtained by the reaction ofmaleic acid or anhydride with an alcohol such as is illustrated above toform a mono- or di-ester of maleic acid and then the reaction of thisester with an olefin or a chlorinated hydrocarbon such as is illustratedabove. They may also be obtained by first esterifying itaconic anhydrideor acid and subsequently reacting the ester intermediate with an olefinor a chlorinated hydrocarbon under conditions similar to those describedhereinabove.

The following specific illustrative examples describe the preparation ofexemplary detergent/dispersants useful in the compositions of thisinvention.

EXAMPLE B-1

A mixture of 906 parts of an oil solution of an alkyl phenyl sulfonicacid (having an average molecular weight of 450, vapor phase osmometry),564 parts mineral oil, 600 parts toluene, 98.7 parts magnesium oxide and120 parts water is blown with carbon dioxide at a temperature of 78°-85°C. for seven hours at a rate of about 3 cubic feet of carbon dioxide perhour. The reaction mixture is constantly agitated throughout thecarbonation. After carbonation, the reaction mixture is stripped to 165°C./20 torr and the residue filtered. The filtrate is an oil solution ofthe desired overbased magnesium sulfonate having a metal ratio of about3.

EXAMPLE B-2

A mixture of 323 parts of mineral oil, 4.8 parts of water, 0.74 parts ofcalcium chloride, 79 parts of lime, and 128 parts of methyl alcohol isprepared, and warmed to a temperature of about 50° C. To this mixturethere is added 1000 parts of an alkyl phenyl sulfonic acid having anaverage molecular weight (vapor phase osmometry) of 500 with mixing. Themixture then is blown with carbon dioxide at a temperature of about 50°C. at the rate of about 5.4 lbs. per hour for about 2.5 hours. Aftercarbonation, 102 additional parts of oil are added and the mixture isstripped of volatile materials at a temperature of about 150°-155° C. at50 mm. pressure. The residue is filtered and the filtrate is the desiredoil solution of the overbased calcium sulfonate having calcium contentof about 3.7% and a metal ratio of about 1.7.

EXAMPLE B-3

A polyisobutenyl succinic anhydride is prepared by reacting achlorinated poly(isobutene) (having an average chlorine content of 4.3%and an average of 82 carbon atoms) with maleic anhydride at about 200°C. The resulting polyisobutenyl succinic anhydride has a saponificationnumber of 90. To a mixture of 1,246 parts of this succinic anhydride and100 parts of toluene there is added at 25° C. 76.7 parts of bariumoxide. The mixture is heated to 115° C. and 125 parts of water is addeddrop-wise over a period of one hour. The mixture is then allowed toreflux at 150° C. until all the barium oxide is reacted. Stripping andfiltration provides a filtrate having a barium content of 4.71%.

EXAMPLE B-4

A mixture of 1500 parts of chlorinated poly(isobutene) (of molecularweight of about 950 and having a chlorine content of 5.6%), 285 parts ofan alkylene polyamine having an average composition correspondingstoichiometrically to tetraethylene pentamine and 1200 parts of benzeneis heated to reflux. The mixture's temperature is then slowly increasedover a 4-hour period to 170° C. while benzene is removed. The cooledmixture is diluted with an equal volume of mixed hexanes and absoluteethanol (1:1). This mixure is heated to reflux and a 1/3 volume of 10%aqueous sodium carbonate is added to it. After stirring, the mixture isallowed to cool and the phases separate. The organic phase is washedwith water and stripped to provide the desired polyisobutenyl polyaminehaving a nitrogen content of 4.5%.

EXAMPLE B-5

A mixture of 140 parts of toluene and 400 parts of a polyisobutenylsuccinic anhydride (prepared from the poly(isobutene) having a molecularweight of about 850, vapor phase osmometry) having a saponificationnumber 109, and 63.6 parts of an ethylene amine mixture having anaverage composition corresponding in stoichiometry to tetraethylenepentamine, is heated to 150° C. while the water/toluene azeotrope isremoved. The reaction mixture is then heated to 150° C. under reducedpressure until toluene ceases to distill. The residual acylatedpolyamine has a nitrogen content of 4.7%.

EXAMPLE B-6

To 1,133 parts of commercial diethylene triamine heated at 110°-150° C.is slowly added 6820 parts of isostearic acid over a period of twohours. The mixture is held at 150° C. for one hour and then heated to180° C. over an additional hour. Finally, the mixture is heated to 205°C. over 0.5 hour; throughout this heating, the mixture is blown withnitrogen to remove volatiles. The mixture is held at 205°-230° C. for atotal of 11.5 hours and then stripped at 230° C./20 torr to provide thedesired acylated polyamine as a residue containing 6.2% nitrogen.

EXAMPLE B-7

To a mixture of 50 parts of a polypropyl-substituted phenol (having amolecular weight of about 900, vapor phase osmometry), 500 parts ofmineral oil (a solvent refined paraffinic oil having a viscosity of 100SUS at 100° F.) and 130 parts of 9.5% aqueous dimethylamine solution(equivalent to 12 parts amine) is added drop-wise, over an hour, 22parts of a 37% aqueous solution of formaldehyde (corresponding to 8parts aldehyde). During the addition, the reaction temperature is slowlyincreased to 100° C. and held at that point for three hours while themixture is blown with nitrogen. To the cooled reaction mixture is added100 parts toluene and 50 parts mixed butyl alcohols. The organic phaseis washed three times with water until neutral to litmus paper and theorganic phase filtered and stripped to 200° C./5-10 torr. The residue isan oil solution of the final product containing 0.45% nitrogen.

EXAMPLE B-8

A mixture of 140 parts of a mineral oil, 174 parts of a poly(isobutene)(molecular weight 1000)-substituted succinic anhydride having asaponification number of 105 and 23 parts of isostearic acid is preparedat 90° C. To this mixture there is added 17.6 parts of a mixture ofpolyalkylene amines having an overall composition corresponding to thatof tetraethylene pentamine at 80°-100° C. throughout a period of 1.3hours. The reaction is exothermic. The mixture is blown at 225° C. withnitrogen at a rate of 5 pounds per hour for 3 hours whereupon 47 partsof an aqueous distillate is obtained. The mixture is dried at 225° C.for 1 hour, cooled to 100° C. and filtered to provide the desired finalproduct in oil solution.

EXAMPLE B-9

A substantially hydrocarbon-substituted succinic anhydride is preparedby chlorinating a polyisobutene having a molecular weight of 1000 to achlorine content of 4.5% and then heating the chlorinated polyisobutenewith 1.2 molar proportions of maleic anhydride at a temperature of150°-220° C. The succinic anhydride thus obtained has an acid number of130. A mixture of 874 grams (1 mole) of the succinic anhydride and 104grams (1 mole) of neopentyl glycol is mixed at 240°-250° C./30 mm. for12 hours. The residue is a mixture of the esters resulting from theesterification of one and both hydroxy radicals of the glycol. It has asaponification number of 101 and an alcoholic hydroxyl content of 0.2%.

EXAMPLE B-10

The di-methyl ester of the substantially hydrocarbon-substitutedsuccinic anhydride of Example 1 is prepared by heating a mixture of 2185grams of the anhydride, 480 grams of methanol, and 1000 cc. of tolueneat 50°-65° C. while hydrogen chloride is bubbled through the reactionmixture for 3 hours. The mixture is then heated at 60°-65° C. for 2hours, dissolved in benzene, washed with water, dried and filtered. Thefiltrate is heated at 150° C./60 mm. to rid it of volatile components.The residue is the defined dimethyl ester.

EXAMPLE B-11

A carboxylic acid ester is prepared by slowly adding 3240 parts of ahigh molecular weight carboxylic acid (prepared by reacting chlorinatedpolyisobutylene and acrylic acid in a 1:1 equivalent ratio and having anaverage molecular weight of 982) to a mixture of 200 parts of sorbitoland 1000 parts of diluent oil over a 1.5-hour period while maintaining atemperature of 115°-125° C. Then 400 parts of additional diluent oil areadded and the mixture is maintained at about 195°-205° C. for 16 hourswhile blowing the mixture with nitrogen. An additional 755 parts of oilare then added, the mixture cooled to 140° C., and filtered. Thefiltrate is an oil solution of the desired ester.

EXAMPLE B-12

An ester is prepared by heating 658 parts of a carboxylic acid having anaverage molecular weight of 1018 (prepared by reacting chlorinatedpolyisobutene with acrylic acid) with 22 parts of pentaerythritol whilemaintaining a temperature of about 180°-205° C. for about 18 hoursduring which time nitrogen is blown through the mixture. The mixture isthen filtered and the filtrate is the desired ester.

EXAMPLE B-13

To a mixture comprising 408 parts of pentaerythritol and 1100 parts oilheated to 120° C., there is slowly added 2946 parts of the acid ofExample B-9 which has been preheated to 120° C., 225 parts of xylene,and 95 parts of diethyleneglycol dimethylether. The resulting mixture isheated at 195°-205° C., under a nitrogen atmosphere and refluxconditions for eleven hours, stripped to 140° C. at 22 mm. (Hg)pressure, and filtered. The filtrate comprises the desired ester. It isdiluted to a total oil content of 40%.

In its broadest concept, the invention relates to two-cycle lubricantsand lubricant-fuels containing the phenolic compounds (A). Suchlubricant and lubricant fuels generally will contain from about one to30 parts by weight of the phenolic compound per hundred parts of oil. Ina preferred concept, the invention relates to further improved two-cyclelubricants and lubricant-fuel oils containing a mixture of the phenoliccompounds (A) and the detergent/dispersants (B).

These oil compositions contain about one to about 30%, typically about 5to about 20%, of at least one phenolic compound (A) as describedhereinabove and about 1 to about 30%, typically 2 to about 20% of atleast one detergent/dispersant (B). The weight ratio of phenol todetergent/dispersant in these oils varies between about 1:10 to about10:1. Other additives such as viscosity index (VI) improvers, lubricityagents, anti-oxidants, coupling agents, pour point depressing agents,extreme pressure agent, color stabilizers and anti-foam agents can alsobe present.

Polymeric VI improvers have been and are being used as bright stockreplacement to improve lubricant film strength and lubrication and/or toimprove engine cleanliness. Dye may be used for identification purposesand to indicate whether a two-cycle fuel contains lubricant. Couplingagents such as organic surfactants are incorporated into some productsto provide better component solubilities and improved fuel/lubricantwater tolerance.

Anti-wear and lubricity improvers, particularly sulfurized sperm oilsubstitutes and other fatty acid and vegetable oils, such as castor oil,are used in special applications, such as racing and for very highfuel/lubricant ratios. Scavengers or combustion chamber depositmodifiers are sometimes used to promote better spark plug life and toremove carbon deposis. Halogenated compounds and/orphosphorus-containing materials may be used for this application.

Rust and corrosion inhibitors of all types are and may be incorporatedinto two-cycle oil formulations. Odorants or deodorants are sometimesused for aesthetic reasons.

Lubricity agents such as synthetic polymers (e.g., polyisobutene havinga number average molecular weight in the range of about 750 to about15,000, (as measured by vapor phase osmometry or gel permeationchromatography), polyol ether (e.g.,poly(oxyethylene-oxypropylene)ethers) and ester oils (e.g., the esteroils described above) can also be used in the oil compositions of thisinvention. Natural oil fractions such as bright stocks (the relativelyviscous products formed during conventional lubricating oil manufacturefrom petroleum) can also be used for this purpose. They are usuallypresent in the two-cycle oil in the amount of about 3 to about 20% ofthe total oil composition.

Diluents such as petroleum maphthas boiling at the range of about30°-90° (e.g., Stoddard solvent) can also be included in the oilcompositions of this invention, typically in the amount of 5 to 25%.

Table B describes several illustrative two-cycle engine oil lubricantcompositions of this invention.

                  TABLE B                                                         ______________________________________                                        TWO-CYCLE ENGINE OIL BLENDS                                                   Phenol of      Detergent/Dispersant                                                                         Oil.sup.2                                       Example                                                                              Example A-1 Example  Amount.sup.1                                                                          Amount, pbw                               ______________________________________                                        A      6           B-2      2       92                                        B      4.5         B-2      1.5     94                                        C      10.6        B-6      2.1     87.3                                      D      7.5         B-4      3.5     89                                        E      6           B-3      2       92                                        F      15          B-5      3       82                                        G      14.2        --       --      85.8                                      ______________________________________                                         .sup.1 Part by weight of the oil solution described in the indicated          Examples.                                                                     .sup.2 The same base oil is used in each blend; this oil is a 650 neutral     solvent extracted paraffinic oil cut with 20 percent by volume Stoddard       solvent and containing 9 pbw per hundred parts of final blend of a bright     stock having a viscosity of 15 0 SUS at 100° C.                   

In some two-cycle engines the lubricating oil can be directly injectedinto the combustion chamber along with the fuel or into the fuel justprior to the time the fuel enters the combustion chamber. The two-cyclelubricants of this invention can be used in this type of engine.

As is well known to those skilled in the art, two-cycle enginelubricating oils are often added directly to the fuel to form a mixtureof oil and fuel which is then introduced into the engine cylinder. Suchlubricant-fuel oil mixtures are within the scope of this invention. Suchlubricant-fuel blends generally contain per 1 part of oil about 15-250parts fuel, typically they contain 1 part oil to about 50-100 partsfuel.

The fuels used in two-cycle engines are well known to those skilled inthe art and usually contain a major portion of a normally liquid fuelsuch as hydrocarbonaceous petroleum distillate fuel (e.g., motorgasoline as defined by ASTM Specification D-439-73). Such fuels can alsocontain non-hydrocarbonaceous materials such as alcohols, ethers,organonitro compounds and the like (e.g., methanol, ethanol, diethylether, methyl ethyl ether, nitromethane) are also within the scope ofthis invention as are liquid fuels derived from vegetable or mineralsources such as corn, alfalfa, shale and coal. Examples of such fuelmixtures are combinations of gasoline and ethanol, diesel fuel andether, gasoline and nitromethane, etc. Particularly preferred isgasoline, that is, a mixture of hydrocarbons having an ASTM boilingpoint of 60° C. at the 10% distillation point to about 205° C. at the90% distillation point.

Two-cycle fuels also contain other additives which are well known tothose of skill in the art. These can include anti-knock agents such astetra-alkyl lead compounds, lead scavengers such as halo-alkanes (e.g.,ethylene dichloride and ethylene dibromide), dyes, cetane improvers,anti-oxidants such as 2,6-di-tertiary-butyl-4-methylphenol, rustinhibitors, such as alkylated succinic acids and anhydrides,bacteriostatic agents, gum inhibitors, metal deactivators, demulsifiers,upper cylinder lubricants, antiicing agents and the like. The inventionis useful with lead-free as well as lead-containing fuels.

An example of a lubricant-fuel composition encompassed by this inventionis a blend of motor gasoline and the lubricant blend described above inExample C in ratio (by weight) of 50 parts gasoline to 1 part lubricant.

Concentrates containing the compositions of this invention are alsowithin the scope of this invention. These concentrates usually compriseabout 20 to about 80% of one or more of the hereinabove described oilsand about 20 to about 80% of one or more phenolic compounds with andwithout the detergent/dispersants. As will be readily understood bythose skilled in the art, such concentrates can also contain one or moreof the hereinabove described auxiliary additives of various types.Illustrative of these inventive concentrates are the following:

EXAMPLE H

A concentrate for treating 2-cycle engine oils is prepared by blendingat room temperature 78.2 parts of the oil solution described in ExampleA-1 with 21.8 parts of the oil solution described in Example B-2.

What is claimed is:
 1. A lubricant composition for two-cycle enginescomprising a major amount by weight of at least one oil of lubricatingviscosity and a minor amount, sufficient to control piston ring stickingand promote general engine cleanliness, of(A) at least one phenoliccompound of the formula

    (R).sub.a --Ar--(OH).sub.b

wherein R is a substantially saturated hydrocarbon-based group of anaverage at least 10 aliphatic carbon atoms; a and b are eachindependently an integer of one up to three times the number of aromaticnuclei present in Ar with the proviso that the sum of a and b does notexceed the unsatisfied valences of Ar; and Ar is a single ring, a fusedor a linked polynuclear ring aromatic moiety having 0 to 3 optionalsubstituents selected from the group consisting of lower alkyl, loweralkoxyl, halo and combinations of two or more of said optionalsubstituents.
 2. The composition of claim 1 wherein R contains anaverage of at least 30 and up to about 400 aliphatic carbon atoms. 3.The composition of claim 2 wherein R is derived from homopolymerized orinterpolymerized C₂ -C₁₀ olefins.
 4. The composition of claim 1 whereinthere are no optional substituents attached to Ar.
 5. The composition ofclaim 1 wherein the phenolic compound (A) is an alkylated phenol of theformula ##STR29## wherein R' is a substantially saturatedhydrocarbon-based substituent having an average of from about 10 toabout 400 aliphatic carbon atoms, R" is a member selected from the groupconsisting of lower alkyl, lower alkoxyl, and halo; and z is from 0 to2.
 6. The composition of claim 5 wherein z is
 0. 7. The composition ofclaim 1 also containing a minor amount of a detergent/dispersant.
 8. Alubricant composition for two-cycle engines comprising a major amount byweight of at least one oil of lubricating viscosity and a minor amount,sufficient to control piston ring sticking and promote general enginecleanliness, of(A) at least one phenolic compound of the formula

    (R).sub.a --Ar--(OH).sub.b

wherein R is a substantially saturated hydrocarbon-based group of anaverage of at least 10 aliphatic carbon atoms; a and b are eachindependently an integer of one up to three times the number of aromaticnuclei present in Ar with the proviso that the sum of a and b does notexceed the unsatisfied valences of Ar; and Ar is a single ring, a fusedring or a linked polynuclear aromatic moiety having 0 to 3 optionalsubstituents selected from the group consisting of lower alkyl, loweralkoxyl, halo and combinations of two or more of said optionalsubstituents; and (B) at least one detergent-dispersant selected fromthe group consisting ofi. at least one neutral or basic metal salt of anorganic sulfur acid, phenol or carboxylic acid; ii. at least onehydrocarbyl-substituted amine wherein the hydrocarbyl substituent issubstantially aliphatic and contains at least 12 carbon atoms; iii. atleast one acylated, nitrogen-containing compound having a substituent ofat least 10 aliphatic carbon atoms made by reacting a carboxylic agantwith at least one amino compound containing at least one

    --NH--

group, said acylating agent being linked to said amino compound throughan imido, amido, amidine, or acyloxy ammonium linkage; iv. at least onenitrogen-containing condensate of a phenol, aldehyde and amino compoundhaving at least one

    --NH--

group; and v. at least one ester of a substituted polycarboxylic acid.9. The composition of claim 8 wherein R contains an average of at least30 and up to about 400 aliphatic carbon atoms.
 10. The composition ofclaim 8 wherein there are no optional substituents attached to Ar. 11.The composition of claim 8 wherein a and b each are
 1. 12. Thecomposition of claim 8 wherein the phenolic compound (A) is an alkylatedphenol of the formula ##STR30## wherein R' is a substantially saturatedhydrocarbon-based substituent having an average of from about 10 toabout 400 aliphatic carbon atoms, R" is a member selected from the groupconsisting of lower alkyl, lower alkoxyl, and halo; and z is 0 to
 2. 13.The composition of claim 12 wherein R' is a purely hydrocarbyl aliphaticgroup of at least about 50 carbon atoms and is derived from a polymer orinterpolymer of an olefin selected from the group consisting of C₂ -C₁₀1-mono olefins and mixtures thereof.
 14. The composition of claim 13wherein z is
 0. 15. The composition of claim 8 wherein thedetergent/dispersant is at least one alkaline earth metal sulfonate. 16.The composition of claim 15 wherein the sulfonate is analkyl-substituted benzene sulfonate wherein the alkyl group has at leastabout 8 carbon atoms.
 17. The composition of claim 8 wherein thedetergent/dispersant is at least one hydrocarbyl-substituted amine. 18.The composition of claim 8 wherein the detergent/dispersant is (iii) atleast one acylated, nitrogen-containing compound having a substituent ofat least 10 aliphatic carbon atoms and made by reacting a carboxylicacylating agent with at least one amino compound containing at least one

    --NH--

group, said acylating agent being linked to said amino compound throughan imido, amido, amidine or acyloxy ammonium linkage.
 19. Thecomposition of claim 18 wherein the amino compound is an alkylenepolyamine of the general formula ##STR31## wherein U is an alkylenegroup of 2 to 10 carbon atoms; each R''' is independently a hydrogenatom, a lower alkyl group or a lower hydroxy alkyl group, with theproviso that at least one R''' is a hydrogen atom, ann n is 1 to
 10. 20.The composition of claim 19 wherein the acylating agent is a mono orpolycarboxylic acid, or reactant equivalent thereof, containing analiphatic hydrocarbyl substituent of at least about 30 carbon atoms. 21.The composition of claim 8 wherein the ratio by weight of phenol to thetotal amount of detergent/dispersant is in the range of about 1:10 toabout 10:1.
 22. In the method for lubricating a two-cycle internalcombustion engine, the improvement which comprises using a lubricantcomposition as claimed in claim
 1. 23. In the method for lubricating atwo-cycle internal combustion engine, the improvement which comprisesusing a lubricant composition as claimed in claim
 7. 24. In the methodfor lubricating a two-cycle internal combustion engine, the improvementwhich comprises using the lubricant composition of claim
 8. 25. Alubricant-fuel mixture for use in two-cycle internal combustion engineswherein the lubricant is the composition of claim
 1. 26. Alubricant-fuel mixture for use in two-cycle internal combustion engineswherein the lubricant is the composition of claim 8.